Protein partial degradation products

ABSTRACT

Novel protein partial degradation products obtainable from grain proteins such as wheat protein, maize protein, soya bean protein, etc., by specific degradation treatments, which are useful as a quality-improving agent for various food stuffs, a surface active agent, a dispersing agent for particles, etc.

This is a divisional of U.S. application Ser. No. 07/593,289, filed Oct.4, 1990, now U.S. Pat. No. 5,138,038, which is a continuation of U.S.application Ser. No. 07/215,727 filed Jul. 6, 1988 (abandoned).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a protein partial degradation product,a process for preparing it, and its use. More particularly, it relatesto a novel protein partial degradation product obtained by degradationof a grain protein such as wheat protein, maize protein, soya beanprotein, etc., a process for preparing the protein partial degradationproduct, and it use as a quality-improving agent for food stuffs or asurface active agent.

2. Description of the Prior Art

Hitherto, as partial degradation products of vegetable proteins, therehas been known those hydrolyzed by an acid, alkali or emzyme. Further,it has been known that such partial degradation products could beobtained also by an oxidative degradation using an oxidizing agent or areductive degradation using a reducing agent.

For instance, Ian L. Batey et al. reported on the properties and theamino acid composition of partial hydrolyzates of wheat gluten obtainedby hydrolysis with an alkali or acid ("Preparation of Salt-Free ProteinProducts from Acid or Alkali-Treated Proteins", Food Chemistry No. 12(1983), Pages 265-275). On the other hand, A. M. Hermansson et al.reported that partial hydrolyzates of rapeseed oil protein obtained byhydrolysis with an alkali, acid or enzyme show some degrees ofsolubility in water, emulsifying and forming properties ("FunctionalProperties of Proteins for Foods--Modification Studies on RapeseedProtein Concentrate", Lebensmittel--Wissenschaft und--Technologie Vol.7, No. 3 (1974), Pages 176-181).

In Japanese Unexamined Patent Publication No. Sho 50-95443, it isdisclosed that the slightly acidic gluten powder obtained from wheatgluten with its acidifying treatment at pH 2.0-6.0 is superior, as anadditive for food stuffs, to one obtained by treatment with a reducingagent. This Publication, however, does not disclose any specific effectof the powder as the additive. Further, it is disclosed in JapaneseUnexamined Patent Publication No. Sho 60-237939 that a wheat glutenpartial hydrolyzate hydrozylate obtained by hydrolysis of wheat glutenwith an enzyme can be used as a substitute for caseinates in theproduction of imitation cheeses.

In Japanese Unexamined Patent Publication No. Sho 53-124654, there isdisclosed a process for the production of processed meat by addition ofa gluten hydrolyzate, which is obtained under an acidic condition withhydrochloric acid, in the form of powder.

On the other hand, it is described in Japanese Unexamined PatentPublications No. Sho 56-8665 and No. Sho 57-79849 that partialdegradation products of a protein, obtained by hydrolysis with an acidor an enzyme, have a surface activate capacity.

Besides, it has been known that hydrolyzates of a protein obtained byhydrolysis with an enzyme is useful for the stabilization of whippeddessert-type products (U.S. Pat. No. 3,889,001 and U.S. Pat. No.3,903,310).

Further, it has been reported recently that a gluten partial hydrolyzateobtained by treating wheat gluten with a pepsin-immobilized bioreactorcan be utilized for improving the quality of baked cake and bread suchas sponge cake (A Japanese paper "Kagaku Kogyo Jiho" issued on Jun. 25,1987).

Thus, various investigation reports have been made as to partialhydrolyzates of vegetable proteins, and in some of them there have beengiven disclosures on the emulsifying capacity and the quality-improvingcapacity for food stuffs of the partial hydrolyzates reported therein.However, according to the result of our confirmation tests, any of thepartial degradation products obtained by subjecting a representativegrain protein such as wheat protein, maize protein, soya been protein,etc. to either of the above-mentioned degradation means could be used asa quality-improving agent for food stuffs or a surface active agent, butits capacity was not of satisfactory level.

On the other hand, polyhydric alcohol/fatty acid ester type surfaceactive agents and lecithin are known as relatively safe surface activeagents, and they are used in the fields of food industry and medicaltreatment and, particularly, used widely as a quality-improving agentfor food stuffs.

For instance, the so-called polyhydric alcohol/fatty acid ester typesurface active agents, such as glycerol/fatty acid ester, propyleneglycol/fatty acid ester, sucrose/fatty acid ester etc. are widely usedas a quality-improving agent for starchy food such as bread or noodle,as the case may be, in combination with ascorbic acid or agluconolactone (Japanese Patent Publication No. Sho 56-42887, JapaneseUnexamined Patent Publications No. Sho 55-118334 and No. Sho 55-118335).Further, it is also proposed to use the glycerol/fatty acid ester, aftersubjecting it to a specific treatment (Japanese Patent Publication No.Sho 59-41379).

Glycerol/fatty acid ester and sucrose/fatty acid ester are frequentlyused as a quality-improving agent for animal proteinic food stuffs usingfish or meat as the main material, such as boiled fish paste, ham,sausage, hamburger, fried ball of mincemeat, etc., and also forvegetable proteinic food stuffs using soya bean protein, wheat glutenand the like as the main material, such as bean-curds, etc. (JapaneseUnexamined Patent Publication No. Sho 53-79058, No. Sho 43-8685 and No.Sho 58-89146).

Polyhydric alcohol/fatty acid ester type surface active agents andlecithin are widely used as a quality-improving agent for creamyprocessed milk products such as coffee whitener, whip cream, ice cream,etc. (Japanese Patent Publications No. Sho 54-39459 and No. Sho51-9823).

Further, polyhydric alcohol/fatty acid ester type surface active agentsand lecithin are used as a quality-improving agent oremulsion-stabilizer for water-in-oil emulsion type food stuffs such asmargarine, shortening, etc., and oil-in-water emulsion type food stuffssuch as dressing, etc. (Japanese Patent Publications No. Sho 51-17150and No. Sho 57-58898).

However, the above-described surface active agents, polyhydricalcohol/fatty acid esters and the like, are chemical synthetic productsin themselves and accordingly their toxicity is uncertain, although theyare approved as food additives. Moreover, these surface active agentsare not necessarily satisfactory with respect to the cost and thequality-improving effect.

Under such circumstances, we have made various investigations and havefound the fact that a hydrolyzate obtained by a two or more-stepdegradation treatment consisting of a combination of an indispensablehydrolysis treatment with alkali by conventional means with one or moredegradation treatments with any of acid, enzyme, oxidizing agent andreducing agent (i) is novel which is different from known hydrolyzatesand (ii) has a surface activate capacity such as an emulsifying capacityor a surface tension-reducing capacity, and a quality-improving capacityfor food stuffs, which are significantly superior to those of knownhydrolyzates and equal to, or higher than, those of the above-mentionedsucrose/fatty acid esters or lecithin, and further a goodparticles-dispersing capacity.

SUMMARY OF THE INVENTION

Thus, the present invention provides a protein partial degradationproduct which is obtained from a grain protein and is characterized bythe following properties:

(a) its weight average molecular weight (according to the Gel filtrationmethod) is in the range of 500-90000,

(b) its ultraviolet absorption λmax is found near 260-280 nm, and itsinfrared absorption is found near 1400, 1630 and 3400 cm⁻¹,

(c) its isoelectric point is in the range of pH 3.9-5.0,

(d) it has a buffer action (2-25 ml of 1N-hydrochloric acid is requiredfor lowering the pH of 100 ml of its 5% (by weight) aqueous solutionfrom 6 to 2),

(e) it is soluble in water and insoluble in methanol, ethanol, acetoneand ethyl ether,

(f) its appearance is pale yellow-red brown colored powder,

(g) it shows coloration in Xanthoprotein reaction and Ninhydrinreaction,

(h) it has a potent, surface tension-reducing capacity (the surfacetension of pure water at 25° C. is reduced to 50 dyne/cm or less(measured with du Noiiy's tensiometer), by adding 0.1% (by weight) of itto the pure water), and

(i) it has a potent emulsifying capacity (100 g of a mixture of waterand soya bean oil, containing at least 30% (by weight) of soya bean oil,can be emulsified completely, by adding 1 g of it to the mixture).

The protein partial degradation products as specified above are believedto be per se new substances, which are not described in any literatureissued prior to the present invention.

The above-mentioned molecular weight was determined according to the Gelfiltration method using sodium polystyrenesulfonate having a molecularweight of 1600, 6500, 16000, 65000 or 88000, as the standard substance,and Sephadex G-75 or G-100 (from pharmacia Ltd.) as the carrier.

BRIEF EXPLANATION OF THE DRAWINGS

FIGS. 1a, 1b, 1c and 1d are graphs each showing a pH-HCl curve of apartial degradation product of the present invention,

FIGS. 2a, 2b, 3a, 3b, 4a, 4b, 5a and 5b are graphs each showing anoptical characteristic of a partial degradation product of the presentinvention, wherein FIGS. 2a, 3a, 4a and 5a each shows a UV light andvisible light absorption spectrum and FIGS. 2b, 3b, 4b and 5b each showsan IR light absorption spectrum.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The most characteristic property of the protein partial degradationproducts of the present invention, which differentiates them fromhitherto known protein partial degradation products, is theiremulsifying property. That is, the partial degradation products of thepresent invention have an excellent emulsifying capacity which is ableto emulsify 100 g of a mixture of water and soya bean oil, containing atleast 30% (by weight) of soya bean oil, completely, by adding 1 g ofthem to the mixture. The term "at least" used here means that 100 g ofthe mixture containing more than 30% (by weight), for example, 40% (byweight) or 50% (by weight), of soya bean oil can be emulsifiedcompletely, and the "complete emulsification" means that a uniformlyemulsified state is maintained for 10 minutes or more, preferably for 1hour or more, as the mixture is left to stand at room temperature afterthe emulsifying treatment by stirring or the like. Any partialdegradation product known hitherto does not have such a remarkableemulsifying capacity. Therefore, the partial degradation products of thepresent invention are evidently differentiated from the partialdegradation products known hitherto, at least in this respect.

In addition, the protein partial degradation products of the presentinvention contain 0.02-4% (by weight) of amide type nitrogen and 0.2-2%(by weight) of amino type nitrogen.

In the present invention, the term "grain protein" means a proteincontained in grain, and the "grain" here means the seed of wheat andbarley, corns (for example, maize), beans (for example, soya beans) andthe like. Among proteins contained in such grains, wheat proteincontains glutenin and gliadin as the main components and is usuallycalled wheat gluten, and maize protein contains zein as the maincomponent and is usually called maize gluten. They each are a knownsubstance which can be obtained from the corresponding grain byseparation and extraction according to the usual manner. For example, toobtain wheat protein (wheat gluten), wheat flour is kneaded stiffly byadding a small amount of water and then kneaded in a large amount ofwater whereby starch is suspended in water and the gluten-containingportion remains as a sticky lump. By repeating this operation severaltimes while replacing the water with new one, wheat protein is obtainedas a grayish brown sticky lump. For the preparation of the partialdegradation products of the present invention, although such lump can beused as it is, a product obtained by drying, further purifying orpartial modifying of the lump may also be used. Wheat gluten iscommercially available in the form of dry powder. Other commerciallyavailable maize gluten, soya bean protein, etc. may also be used, asconvenient.

These proteins may be used in the form of either crude products orpurified products. However, it is preferable to use a product containingthe protein in an amount of 70% or more.

The partial degradation products of the present invention can beprepared by subjecting the above-mentioned grain protein to a multistepdegradation treatment consisting of a combination of a hydrolysistreatment with alkali with one or more degradation treatments with anyof acid, enzyme, oxidizing agent and reducing agent. That is, thepartial degradation products are obtained by combining a degradationtreatment with alkali with other degradation treatment(s).

The above hydrolysis treatment with alkali is suitably effected byheating the subject protein in a dilute aqueous alkaline solution.Usually, it is suitable to heat an aqueous solution or dispersion of thesubject protein to be hydrolyzed at ca. 60°-180° C. for ca. 10-600minutes while stirring in the presence of an alkaline agent such assodium hydroxide, potassium hydroxide, calcium hydroxide, sodiumcarbonate, potassium carbonate, etc. As the aqueous solution ordispersion of the subject protein to be hydrolyzed, one containing 2-40%(by weight) of the subject protein is preferably used. The amount of analkaline agent used is preferably 0.1-6 g per 20 g of the subjectprotein to be hydrolyzed.

Among other degradation treatments to be effected in combination withthe above-mentioned hydrolysis treatment with alkali, the degradationtreatment with acid is suitably effected by heating the subject in adilute aqueous acid solution. Usually, it is suitable to heat an aqueoussolution or dispersion of the subject protein to be degraded at ca.60°-120° C. for ca. 10-600 minutes while stirring in the presence of aninorganic acid such as hydrochloric acid, sulfuric acid, etc. or anorganic acid such as acetic acid or the like. The quantitativeconditions here are preferably the same as those mentioned above for thealkaline hydrolysis.

The degradation treatment with enzyme is suitably effected in a diluteaqueous solution of an enzyme having protease activity. Usually, it iseffected by keeping an aqueous solution or dispersion of the subjectprotein to be degraded at ca. 10°-60° C. for ca. 60-600 minutes in thepresence of a small amount of an enzyme such as pepsin, alkali protease,papain, etc. under the optimal pH condition for the enzyme. Thequantitative conditions here are preferably the same as those describedabove, except that 0.02-5 g of the enzyme is used per 20 g of thesubject protein to be degraded.

The degradation treatment with reducing or oxidizing agent is suitablyeffected in a dilute aqueous solution of the reducing or oxidizingagent. Usually, it is effected by keeping an aqueous solution ordispersion of the subject to be degraded at ca. 10°-100° C. for ca.10-600 minutes in the presence of a small amount of a reducing agentsuch as a sulfite, a thiol compound, erysorbic acid, hydrazine, etc. oran oxidizing agent such as hydrogen peroxide, a hypochlorite, etc. Thequantitative conditions here are preferably the same as those describedabove, except that 0.1-5 g of the reducing agent or the oxidizing agentis used per 20 g of the subject protein to be degraded.

There is no limitation in the order of effecting the above-mentionedmultiple degradation treatments. That is, the partial degradationproducts of the present invention can be obtained by subjecting thestarting material such as wheat gluten or the like, first to thehydrolysis treatment with alkali (A) and thereafter to one or more ofthe degradation treatments with acid, enzyme, reducing agent oroxidizing agent (degradation treatments with an agent except alkali) (B)or, in reverse order, first to (B) and then to (A). Further, they can beobtained also by subjecting them first to a degradation treatment withan agent except alkali (B), thereafter to the hydrolysis treatment withalkali (A), and again to a degradation treatment with an agent exceptalkali (B). Neutralization treatment may suitably be effected betweenthese treatments.

It has been found that the partial degradation products of the presentinvention thus obtained are high molecular amphoteric electrolyteshaving various interesting properties and actions.

First, it has been confirmed that the partial degradation products haveespecially potent surface-activate capacity and particle (inclusive ofsolid particle and liquid particle) dispersing capacity. In addition,they are considered to have an adsorbing capacity onto particle surface,complex-forming capacity with protein and starch, and the like. Suchproperties and use of the partial degradation products are explainedhereinafter.

(i) They are useful as a surface active agent, mainly because of theirsurface-activate capacity. They have a high HLB and hydrophilicproperty, in addition to their high surface-activate capacity, and arelow foaming. They have the advantage of low toxicity, low price, etc.because they are a kind of modified food stuffs.

There is no special limitation in the fields where they are used as asurface active agent. They can be used in various fields such as foodstuffs, cosmetics, pharmaceutical medicines, agricultural chemicals,etc. Particularly, on the ground of their high HLB, they are useful as adetergent or a solubilizer. For example, they can be used also as asolubilizer for conventional surface active agents less soluble inwater, such as polyhydric alcohol/fatty acid ester type surface activeagents, or lecithin.

(ii) They are useful as a dispering agent for various particles in thefields of food stuffs, cosmetics, agricultural chemical, paper & pulp,paint & varnish, ceramics, etc., because of their particle-dispersingcapacity. They can be applied either as solid particles and liquidparticles. The solid particles may be water-insoluble or sparinglysoluble inorganic particles of calcium carbonate, sachine white, talc,red oxide, cement, magnesium hydroxide, zinc white, barium sulfate,kaolin, clay, etc. or water-insoluble or sparingly soluble organicparticles of cocoa powder, fruit pulp, solid matters of miso (beanpaste), solid matters of soup, powdery agricultural chemicals (forexample, zinc ethylenebis(dithiocarbamate),bis(dimethylthiocarbamoyl)disulfide, tetrachloroisophthalonitrile,N-(trichloromethylthio)-4-cyclo-hexene-1,2-dicarboximide,N-(1,1,2,2,-tetrachloroethylthio)-4-cyclohexene-1,2-dicarboximide,m-tolylmethylcarbamate, 3',4'-dichloropropionanilide,2-chloro-4,6-bis(ethylamino)-1,3,5-triazine,methyl-3,4-dichlorocarbanilate, methylene bisthiocyamate),pharamaceutical medicines, etc. On the other hand, the liquid particlesmay be liquid agricultural chemicals (for example,S-1,2-bis(ethoxycarbonyl)ethyl dimethyl phosphorothiolothionate, diethyl2-isopropyl-4-methyl-6-pyrimidinyl phosphorothionate, etc.) orpharmaceutical medicines.

As to the particle-dispersing capacity of the partial degradationproducts, further detailed explanation is given hereinafter.

For example, it is possible, to reduce the viscosity of a calciumcarbonate slurry containing 50% (by weight) of calcium carbonate and theviscosity of kaolin slurry containing 60% (by weight) of kaolin, each to6000 cps or less by addition of a small amount of the product of theinvention.

Further, it is possible, by addition of them to powdery food stuffs suchas cocoa, instant miso soup, instant soup, instant zenzai (thick redbean-meal soup with sugar), instant shiruko (red-bean soup with sugar),etc., to accelerate dispersion of the contents of the powdery foodstuffs into water and prevent sedimentation of suspended particles(solid matters) for a long time.

As for agricultural chemicals, they prevent aggregation/separation ofthe active ingredient particles in flowable preparations, emulsionpreparations and aqueous solution preparations for a long time, as theyare used on preparing these preparations, and accelerate dispersion ofthe active ingredient particles and the carrier into water and preventsedimentation of the particles for a long time, as the preparationsmentioned above or wettable preparations containing them are dilutedwith water.

(iii) They are useful as a quality-improving agent for various foodstuffs, because they have a complex-forming capacity with protein andstarch, in addition to the surface-activate capacity and theparticle-dispersing capacity.

1 They are useful as a quality-improving agent for starchy food stuffs.

For example, they have quality-improving effects such as the so-calledaging-preventing effect which prevents or suppresses the hardening ofbread and noodles due to the degeneration of starch; a water-holdingproperty-improving effect which prevents or retards the hardening ofbread and noodles due to drying; a dough-regulating effect whichregulates fineness and stickiness of the dough suitably on making breadand noodles, promotes the rising of dough due to the fermentation withyeast on making bread and, as a result, provides bread having fine anduniform cellular texture; and the like.

On making bread, they are suitably added to the material in an amount of0.01-5% (by weight) of wheat flour. By such addition, the dough becomessmooth and is improved in its water-holding property and its aging isprevented or suppressed. Moreover, the cellular texture of the breadobtained becomes fine and uniform, and the volume of the bread obtainedis much increased compared with the use of conventionalquality-improving agents. When they are used in an amount less than0.01% (by weight), the quality-improving effect is not revealed well. Onthe other hand, addition in an amount more than 5% (by weight) is alsonot preferable, any effect compensating the economical demerit being notbrought about. Usually, it is preferred to use the products of theinvention in an amount of 0.05-3% (by weight), particularly 0.1-1% (byweight), in view of the total quality-improving effect and the cost.However, when the main purpose of using them resides in the regulationof dough and the increase in the volume of bread, an amount of some0.02-1.0% (by weight) is sufficient. On the other hand, when the mainpurpose resides in the improvement in preventing the aging of bread, itis preferred to use them in an amount of 0.05% (by weight) or more.

For making noodles, they are suitably added to the material in an amountof 0.01-5% (by weight), preferably 0.05-3% (by weight), of the wheat,buckwheat, rice rye, rye, maize, or the like.

By adding the products of the invention, it is possible to prevent orsuppress the aging of noodles, to improve the palatability and theloosening of noodles, and also to improve the yield of noodles on makingand the preservability of the resulting noodles. Further, it is possibleby addition of the products of the invention to accelerate therestoration of dried noodles and instant noodles, and also to preventadhesion to the packing material of packed, boiled noodles.

2 They are useful as a quality-improving agent for proteinic food stuffs(containing protein as the main component in an amount of 40% (byweight) of the total solid matters).

For example, on preparing animal proteinic food stuffs containing fishor meat as the main material, such as boiled fish paste or ham, sausage,hamburger, fried ball of mincemeat, etc., it is possible by using asuitable amount of them to obtain those proteinic food stuffs which havean improved shaping property, a good shape-keeping property and textureand an improved palatability. Further, it is also possible because ofsuch quality-improving effect to increase the amount of vegetableprotein incorporated into the animal proteinic food stuffs, which hasbeen hitherto limited to at the most 10% (by weight) or so, because ofits dispersibility. Furthermore, they reveal a quality-improving effectalso on vegetable proteinic food stuffs such as soya bean proteinic foodstuffs, bean-curds, etc. by adding them to the vegetable proteinic foodstuffs on the preparation thereof. By the addition of the products ofthe invention, the stability, the shape-keeping property and the textureof soya bean proteinic food stuffs are improved and the elasticity ofsoya bean-curds is enhanced. The amount of addition in these cases issuitably 0.05-10% (by weight), preferably 0.5-5% (by weight), of thematerial of the proteinic food stuffs. With an amount less than 0.5% (byweight), the above-mentioned various quality-improving effects are notrevealed sufficiently and, with an amount more than 10% (by weight), thequality-improving effects attained do not correspond to the costincreased.

3 They are useful as a quality-improving agent for creamy processed milkproduct.

The creamy processed milk products here include, besides therepresentative ones such as the above-mentioned coffee whitener, whipcream, ice cream, etc., those liquid foamy food stuffs which contain atleast solid matters of milk, oils and fats, and water as theirindispensable components.

For example, although a raw cream obtained from milk or a processed milkproduct containing solid matters of milk, skim milk, etc., oils andfats, and water as its main components, is used, by itself, as coffeewhitener and, by making it to hold air by agitation, as whip cream; byaddition of the partial degradation products of the present invention tothe former, a coffee whitener which is suppressed in the featheringphenomenon and the generation of surface fatty film can be provided inconvenience and, by addition to the latter, a foamy product (whip) whichis stabilized and has a good shape-keeping property can be provided asconvenient. Further, the partial degradation products reveal alsovarious quality-improving effects on ice cream, such as stabilization ofthe shape-keeping property, etc.

The amount of addition here is suitably 0.02-5% (by weight), preferably0.1-2% (by weight), per the materials (total solid matters) of theprocessed milk product. Addition of an amount less than 0.02 (by weight)gives insufficient quality-improving effect, and addition of an amountmore than 5% (by weight) does not bring about any merit of effect whichcorresponds to the elevated cost.

4 They are useful as a quality-improving agent for emulsified oily foodstuffs.

The emulsified oily food stuffs here include, besides the representativeones such as margarine, shortening, dressing, etc., those various oilyfood stuffs in which the oily phase and the aqueous phase are kept atleast at a state of emulsion.

For example, in solid-type emulsified oily food stuffs, they reveal aquality-improving effect such as an effect of making the constitution ofoily phase and aqueous phase fine and simultaneously suppressing theseparation of the two phases which may occur on dissolution, and thelike. In fluid or semifluid emulsified oily food stuffs such asdressings, etc., they reveal an effect of keeping the stabilizedemulsion state for a prolonged time. Further, the stabilizers accordingto the present invention give an effect of suppressing the separation ofoily phase and aqueous phase which may occur on preparing emulsifiedoily food stuffs and the various damages resulting from such separation.

The amount of addition is suitably 0.01-5% (by weight), preferably0.03-2% (by weight), per the total amount of the emulsified oily foodstuffs, in view of the effect of stabilizing the emulsion and the effectof making the dispersed phase fine. Addition of an amount less than0.01% (by weight) does not reveal the above effect sufficiently, andaddition of an amount more than 5% (by weight) is economicallyunsuitable, not bringing about any effect corresponding to the increasedamount.

Each of the effects 1-4 as described above is superior to that attainedby conventionally used surface active agents or usual grain proteinpartial degradation products.

Although the protein partial degradation products of the presentinvention can be used as a surface active agent, a dispersing agent, ora quality-improving agent for various food stuffs, in the form of theiraqueous solution obtained by the degradation treatment, it is alsopossible to use them in the form of powder which is obtained by dryingand pulverizing the aqueous solution. It is also suitable to use theirpurified products obtained by desalting treatment such asultra-filtration, etc., or decoloring treatment.

Among the protein partial degradation products of the present invention,those having an average molecular weight of 17000-70000 have asurface-activating capacity higher than the sucrose/fatty acid estersand accordingly are especially useful as a surface active agent, andthose having an average molecular weight of 700-70,000 have a highparticle-dispersing capacity and a high quality-improving capacity forfood stuffs and are especially useful as a particle-dispersing agent ora quality-improving agent for food stuffs.

The partial degradation products of the present invention may be used incombination with other known surface active agents, in accordance withthe purpose of use. As such known surface active agents, relativelyoleophilic surface active agents, i.e., polyhydric alcohol/fatty acidesters, such as monoglycerides, sorbitan esters, glycol ethers,sucrose/fatty acid esters, etc. and lecithin, and the like are used.Among these known surface active agents, monoglycerides andsucrose/fatty acid esters give various synergistic effects when used incombination with the partial degradation products of the presentinvention in a ratio (by weight) of 1:6-6:1, preferably 1:4-4:1.

Further, the partial degradation products of the present invention maybe used also in combination with the conventional preservatives such asethanol, propionic acid, lactic acid, sorbic acid, dehydroacetic acid,sodium chloride, etc.

On using them as a particle-dispersing agent, other dispersing agents,for example, polysaccharides such as gum arabic, pectin, CMC, gumxanthenic, alginic acid, etc, synthetic high molecular compounds such aspolyacrylic acid, polyvinyl alcohol, etc., and the like, may also beused in combination.

EXAMPLE

The present invention is explained in detail by the following Examplesand Tests.

EXAMPLES 1 TO 12 Preparation of Partial Degradation Products of WheatGluten Treated With Acid, Followed With Alkali

Twenty grams of wheat gluten (a reagent grade from Wako Pure ChemicalsLtd., JAPAN) were added to each of flasks containing 100 g ofhydrochloric acid equivalent to 0.5 g, 1 g, 2 g or 4 g of hydrogenchloride. Each of the mixtures was heated at 80° C. or 100° C. for 60minutes under stirring, neutralized by sodium hydroxide and diluted withpure water into a total weight of 200 g. Thus, four kinds of 10% aqueoussolutions of wheat glutens partially olegraded by the acid which areshown in Table 1 were obtained. One hundred grams of each of the abovesolutions were put in a flask to which sodium hydroxide or sodiumcarbonate in the range of 0.5 g to 2 g was added. The mixture was heatedat a temperature of 80° C. to 150° C. for a period of 30 minutes to 360minutes, neutralized by hydrochloric acid and diluted with pure waterinto a total weight of 200 g. Thus, Test samples 1 to 12 of partialdegradation products of the present invention were obtained.

Conditions for partial degradation and average molecular weights of thedegradation products are shown in Table 1.

Test sample 1 desalted by precipitation at isoelectric point or dialysiswas almost odorless and tasteless.

EXAMPLES 13 TO 16 Preparation of Partial Products of Maize Gluten andSova Bean Gluten by Treatment With Acid Followed by Alkali

Maize gluten (from Nihon Shokuhin Kako Co., Ltd., JAPAN) as the startingmaterial was put into the same partial degradation treatments with acidand alkali as those employed in Examples 6 and 1, whereby Test samples13 and 14 having a weight average molecular weight of 11,800 and 27,100,respectively were obtained.

Using a soya bean protein prepared by defatting a commercially availabledried soya bean curd (yu ba) with acetone, as a starting material, thepartial degradation treatments with acid and alkali were performed underthe same conditions as those employed in Examples 6 and 1, whereby Testsamples 15 and 16 having a weight average molecular weight of 12,000 and29,000, respectively were obtained.

EXAMPLES 17 AND 18 Preparation of Partial Degradation Products of WheatGluten by Treatment with Alkali, followed With Acid

                                      TABLE 1                                     __________________________________________________________________________                          Addition of                                             Test                                                                              Addition of       sodium             Average                              sample                                                                            hydrogen                                                                            Temperature                                                                          Time hydroxide                                                                            Temperature                                                                          Time molecular                            No. chloride (g)                                                                        (°C.)                                                                         (minute)                                                                           (g)    (°C.)                                                                         (minute)                                                                           weight                               __________________________________________________________________________    1   1     100    60   0.5    100    60   48000                                2   1     100    60   1      100    60   41000                                3   1     100    60   2      100    60   16500                                4   1     100    60   2      150    360   980                                 5   2     100    60   0.5    100    60   42200                                6   2     100    60   1      100    60   22000                                7   2     100    60   2      100    60   15000                                8   2     100    60   2      150    360   870                                 9   4     100    60   1      100    60   18000                                10  4     100    60   2      150    360   670                                 11  2     100    60   Addition of                                                                          100    60   42200                                                      sodium                                                                        carbonate (g)                                                                 1                                                       12  0.5   80     60   0.5    80     30   79000                                __________________________________________________________________________

Twenty grams of the same wheat gluten as used in Examples 1 to 12 wereadded to 100 g of an aqueous solution containing 2 g or 4 g of sodiumhydroxide. Each of the mixture was heated at 100° C. for 60 minutes withstirring, neutralized by hydrochloric acid and diluted with pure waterinto a total weight of 200 g. Thus, 10% aqueous solutions of wheatgluten paritally degraded by the alkali were obtained. To 100 g of eachof the above solutions was added hydrochloric acid equivalent to 0.5 gor 1 g of hydrogen chloride and the resultant was heated at 100° C. for60 minutes with stirring, neutralized by sodium hydroxide and dilutedwith pure water into a total weight of 200 g. Thus, Test samples 17 and18 shown in Table 2 were obtained.

Conditions for partial degradation and average molecular weights of thedegradation products are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________    Degradation by alkali  Degradation by acid                                        Addition of        Addition of        Average                             Test                                                                              sodium Temperature                                                                          Time hydrochloric                                                                         Temperature                                                                          Time molecular                           sample                                                                            hydroxide (g)                                                                        (°C.)                                                                         (minute)                                                                           acid (g)                                                                             (°C.)                                                                         (minute)                                                                           weight                              __________________________________________________________________________    17  2      100    60   0.5    100    60   38200                               18  4      100    60   1      100    60   13200                               __________________________________________________________________________

EXAMPLES 19 AND 20 Preparation of Partial Degradation Products of WheatGluten Treated With Enzyme, Followed With Alkali

Twenty grams of the same wheat gluten as used in Examples 1 to 12 wereadded to a flask containing 150 g of 0.1N hydrochloric acid to obtain anaqueous solution of pH 1.5. The solution was treated with 2.2 g ofpepsin and warmed at 37° C. for 90 minutes under stirring. The resultantwas neutralized by sodium hydroxide and diluted with pure water into atotal weight of 200 g to obtain a 10% aqueous solution of wheat glutenpartially degraded by the enzyme. To two flasks containing 100 g of theabove solution were added 1 g and 2 g of sodium hydroxide, respectively.The mixtures were heated at 100° C. for 60 minutes under stirring,neutralized by hydrochloric acid and diluted with pure water into atotal weight of 200 g, by which Test samples 19 and 20 were obtained.Test samples 19 and 20 show average molecular weight of 29,000 and14,000, respectively.

EXAMPLE 21 Preparation of Partial Degradation Product of Wheat GlutenTreated With Reducing Agent, Followed by Alkali

Twenty grams of the same wheat gluten as used in Examples 1 to 12 wereadded to 100 g of an aqueous solution containing 4 g of sodium sulfite.The mixture was heated at 30° C. for 60 minutes under stirring anddiluted with pure water into a total weight of 200 g to obtain 10%aqueous solution of wheat gluten partially degraded by the reducingagent. To 100 g of the above solution was added 1 g of sodium hydroxideand the mixture was heated at 100° C. for 60 minutes under stirring,neutralized by hydrochloric acid and diluted with pure water into atotal weight of 200 g, by which Test sample 21 having an averagemolecular weight of 39,500 was obtained.

EXAMPLE 22 Preparation of Partial Degradation Product of Wheat GlutenTreated With Alkali and Enzyme in Reverse Order of Example 19

Twenty grams of the same wheat gluten as used in Examples 1 to 12 wereadded to 100 g of an aqueous solution containing 2 g of sodiumhydroxide. The mixture was heated at 100° C. for 60 minutes understirring, neutralized by hydrochloric acid and diluted with pure waterinto a total weight of 200 g, by which 10% aqueous solution of wheatgluten partially degraded by alkali was obtained. To 100 g of the aboveaqueous solution was added a reagent of hydrochloric acid to obtain anaqueous solution of pH 1.5. The resultant was treated with 0.1 g ofpepsin and heated at 37° C. for 90 minutes. The mixture was neutralizedby sodium hydroxide and diluted with pure water into a total weight of200 g, by which Test sample 22 having an average molecular weight of24,500 was obtained.

EXAMPLE 23 Preparation of Partial Degradation Product of Wheat GlutenTreated With Alkali and Oxidizing Agent

Twenty grams of the same wheat gluten as used in Examples 1 to 12 wereadded to 100 g of an aqueous solution containing 2 g of sodiumhydroxide. The mixture was heated at 100° C. for 60 minutes understirring, neutralized by hydrochloric acid and diluted with pure waterinto a total weight of 200 g, by which 10% aqueous solution of wheatgluten partially degraded by the alkali was obtained. To 100 g of theabove solution was added hydrogen peroxide equivalent to 0.5 g of H₂ O₂.The mixture was heated at 40° C. for 60 minutes under stirring, to whichsodium thiosulfate equivalent to the remaining H₂ O₂ was added. Theresultant was diluted with pure water into a total weight of 200 g, bywhich Test sample 23 having an average molecular weight of 37,000 wasobtained.

The various properties of the partially degraded proteins of the presentinvention obtained in Examples 1 to 23 are shown in Table 3.

                                      TABLE 3                                     __________________________________________________________________________    Test sample No.                                                                              1   2   3   4   5   6   7   8                                  __________________________________________________________________________    Material       W   W   W   W   W   W   W   W                                  Average molecular weight                                                                     48000                                                                             41000                                                                             16500                                                                             980 42200                                                                             22000                                                                             15000                                                                             870                                Isoelectric point                                                                            4.6 4.5 4.4 4.1 4.5 4.3 4.4 4.0                                Buffering [1N-HCl (ml)/5 g]                                                                  10  16  17  22  17  13  18  20                                 action                                                                        Xanthoproteic reaction                                                                       +   +   +   +   +   +   +   +                                  Ninhydrin reaction                                                                           +   +   +   +   +   +   +   +                                  UV λmax. (nm)                                                                         274.0                                                                             275.2                                                                             273.6                                                                             275.1                                                                             272.8                                                                             272.4                                                                             271.6                                                                             273.7                              IR absorption  3400                3400                                                                              3400                                   (cm.sup.-1)    1630                1630                                                                              1630                                                  1400                1400                                                                              1400                                   Amide type nitrogen (%)                                                                      1.63    0.26                                                                              0.07    0.57                                                                              0.18                                   Amino type nitrogen (%)                                                                      0.39    0.48                                                                              0.53    0.43                                                                              0.51                                   __________________________________________________________________________    Test sample No.                                                                              9   10  11  12  13  14  15  16                                 __________________________________________________________________________    Material       W   W   W   W   C   C   B   B                                  Average molecular weight                                                                     18000                                                                             670 42200                                                                             79000                                                                             11800                                                                             27100                                                                             12000                                                                             29000                              Isoelectric point                                                                            4.0 4.1 4.3 4.8 4.2 4.4 4.2 4.3                                Buffering [1N-HCl (ml)/5 g]                                                                  20  22  16  3   17  8   15  8                                  action                                                                        Xanthoproteic reaction                                                                       +   +   +   +   +   +   +   +                                  Ninhydrin reaction                                                                           +   +   +   +   +   +   +   +                                  UV λmax. (nm)                                                                         273.0                                                                             272.8                                                                             271.8                                                                             273.2                                                                             274.0                                                                             273.5                                                                             266.8                                                                             269.1                              IR absorption      3400        3400    3400                                   (cm.sup.-1)        1630        1630    1630                                                      1400        1400    1400                                   Amide type nitrogen (%)                                                                          0.06    2.52                                                                              1.37        0.94                               Amino type nitrogen (%)                                                                          0.54    0.35                                                                              0.39        0.48                               __________________________________________________________________________    Test sample No.    17  18  19  20  21  22  23                                 __________________________________________________________________________    Material           W   W   W   W   W   W   W                                  Average molecular weight                                                                         38200                                                                             13200                                                                             29000                                                                             14000                                                                             39500                                                                             24500                                                                             37000                              Isoelectric point  4.5 4.3 4.2 4.1 4.3 4.2 4.3                                Buffering [1N-HCl (ml)/5 g]                                                                      16  19      18                                             action                                                                        Xanthoproteic reaction                                                                           +   +   +   +   +   +   +                                  Ninhydrin reaction +   +   +   +   +   +   +                                  UV λmax. (nm)                                                                             273.0                                                                             275.2                                                                             271.4                                                                             272.6                                                                             273.5                                                                             273.8                                                                             274.0                              IR absorption              3400    3400                                       (cm.sup.-1)                1630    1630                                                                  1400    1400                                       Amide type nitrogen (%)                                                                              0.81                                                                              2.95    0.91    1.18                               Amino type nitrogen (%)                                                                              0.45                                                                              0.56    0.62                                       __________________________________________________________________________

The symbols of W, C and B used in Table 3 mean wheat gluten, maizegluten and soya bean protein, respectively and the blank in Table 3means "not measured" or "not tested".

The methods of measurement of various properties are as follows.

Average Molecular Weight

The value is determined by Gel Filtration Method using sodiumpolystyrenesulfonates having molecular weight of 1,600, 6,500, 16,000,65,000 or 88,000 as standard substances, and Sephadex G-75 or G-100(available from Pharmacia Ltd.) as the carrier.

Isoelectric Point

One hundred grams of each of Test samples 1 to 23 are put in a beaker,to which each 1 ml portions of 1N-HCl is added at room temperature understirring, while pH value is measured. The value of pH at the point thatthe pH curve becomes a gentle slope is taken as the isoelectric point.

Buffering Action

The amount of 1N-HCl required to lower the pH from 6 to 2 on the curveobtained in the measurement of the isoelectric point is taken as thevalue of the buffering action. The curves for Test samples 1, 7, 13 and15 are shown in FIGS. 1a, 1b, 1c and 1d.

UV Absorption

UV absorbance is measured in the range of 800-200 nm by use of theHitachi U-3200 type spectrophotometer.

IR Absorption

IR absorbance is measured by the KBr method using the Hitachi 216-10type IR spectrophotometer. (Amido type nitrogen and amino type nitrogen)

Pretreatment

The test sample is concentrated in vacuo under an alkaline condition toremove ammonia before the following measurements.

Amide Type Nitrogen

A portion of the sample is subjected to thermal decomposition in ahydrochloric acid solution. The resultant is adjusted with sodiumhydroxide to pH 10 and distilled. The value is obtained by measuring thedistillate using the spectrophotometry (JIS K0102 Indophenol method).

Amino Type Nitrogen

1N-HCl is gradually added to a portion of the sample to obtain a pH-HClcurve. From the curve, the amount (a ml) of 1N-HCl required to lower thepH from 11 to 5 is obtained.

On the other hand, 1N-HCl is added to the other same amount of thesample into pH 6.8 and then 37% formaldehyde solution is added (about2.5 times as much as the amount of the sample). The pH of the resultingsolution is increased to more than 11 by addition of 1N-NaOH and then1N-HCl is added to obtain a pH-HCl curve, from which the amount (b ml)of 1N-HCl required to lower the pH from 11 to 5 is obtained (FormolTitration Method). Further 37% formalin solution in the same amount asused above is titrated with 1N-HCl in the same manner as in the abovetitration to obtain a pH-HCl curve, from which the amount (c ml) of1N-HCl required to lower the pH from 11 to 5 is obtained.

The amount of amino type nitrogen is obtained from the value of a-(b-c)ml. Each of the measurements is expressed as % by weight with respect tothe sample.

COMPARATIVE EXAMPLES 1 TO 3 Preparation of Partial Degradation Productsof Wheat Gluten by Acid

Twenty grams of wheat gluten (a reagent grade from Wako Pure ChemicalsLtd., JAPAN) were added to each of three flasks containing 100 g ofhydrochloric acid containing 1 g, 2 g and 4 g of hydrogen chloride. Eachof the mixtures was heated at 100° C. for 60 minutes under stirring,neutralized by sodium hydroxide and diluted with pure water into a totalweight of 200 g to obtain Comparative test samples 1 to 3 containing apartial degradation product.

Conditions for the degradation and weight average molecular weights ofthe degradation products are shown in Table 4.

                  TABLE 4                                                         ______________________________________                                        Comparative                                                                            Addition of                 Average                                  test sample                                                                            hydrochloric                                                                             Temperature                                                                              Time  molecular                                No.      acid (g)   (°C.)                                                                             (min.)                                                                              weight                                   ______________________________________                                        1        1          100        60    91,000                                   2        2          "          "     64,000                                   3        4          "          "     47,000                                   ______________________________________                                    

COMPARATIVE EXAMPLE 4 Preparation of Partial Degradation Product ofWheat Gluten by Enzyme

Twenty grams of the same wheat gluten as used in Comparative example 1were added to a flask containing 150 g of 1N hydrochloric acid to obtainan aqueous solution of pH 1.5. The gluten in the solution was treatedwith 0.2 g of pepsin and warmed at 37° C. for 90 minutes under stirring.The resultant was neutralized by sodium hydroxide and diluted with purewater into a total weight of 200 g to obtain Comparative test sample 4having an average molecular weight of 60,000.

COMPARATIVE EXAMPLE 5 Preparation of Partial Degradation Product ofWheat Gluten by Reducing Agent

Twenty grams of the same wheat gluten as used in Comparative example 1were added to 100 g of an aqueous solution containing 4 g of sodiumsulfite. The mixture was heated at 30° C. for 60 minutes under stirringand diluted with pure water into a total weight of 200 g to obtainComparative test sample 5 having an average molecular weight of 79,000.

COMPARATIVE EXAMPLES 6 TO 9 Preparation of Partial Degradation Productof Wheat Gluten by Alkali

Twenty grams of the same wheat gluten as used in Comparative example 1were added to each of four flasks containing 100 g of a solutioncontaining sodium hydroxide in the range of 0.2 g to 4 g. The mixtureswere thoroughly mixed and were heated at a temperature of 80° C. to 100°C. for a period of 30 minutes to 60 minutes under stirring. Theresultants were neutralized by hydrochloric acid and diluted with purewater into a total weight of 200 g to obtain Comparative test samples 6to 9.

Conditions for degradation and average molecular weights of thedegradation products are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                        Comparative                                                                            Addition                    Average                                  test sample                                                                            of sodium  Temperature                                                                              Time  molecular                                No.      hydroxide (g)                                                                            (°C.)                                                                             (min.)                                                                              weight                                   ______________________________________                                        6        2          100        60    47,000                                   7        4          "          "     20,200                                   8        0.5         80        30    80,500                                   9        0.2        "          "     101,000                                  ______________________________________                                    

The following tests were carried out on Test samples of the presentinvention and Comparative test samples.

TEST 1 Determination of Surface Tension

Of Test samples and Comparative test samples prepared in Examples andComparative examples, respectively, a sucrose fatty acid ester(Comparative test sample 10) and soya bean lecithin (Comparative testsample 11), the values of surface tension are determined with du Nouy'stensiometer using pure water (solvent) at 25° C. The results are shownin Table 6. The used sucrose fatty acid ester has the trade name, DKester F-160 (HLB:15) from DAI-ICHI KOGYO SEIYAKU CO., Ltd., JAPAN andthe used soya bean lecithin the trade name, Honen lecithin AY from HonenSeiyu Co., Ltd., JAPAN.

TEST 2 Determination of Emulsified State Maintaining Time

Of Test samples and Comparative test samples prepared in Examples andComparative examples, a sucrose fatty acid ester and soya bean lecithin,the emulsified state maintaining time is determined by the followingmethod. The results are shown in Table 6.

Test Method

The reagent and city water are put into a beaker into a total weight of70 g so that the mixture is adjusted to pH 7.0 and 30 g of soya bean oil(a reagent from Kishida Kagaku Co., Ltd., JAPAN) are added. Theresultant is mixed for 5 minutes by a homomixer at 8000 rpm. Immediatelyafter mixing the emulsion is transferred into a color comparison tubeand left at room temperature. The time required until separation of theemulsion begins is defined as an emulsified state maintaining time. Theconcentration of a partial degradation product of the present inventionis 1.0% by weight with respect to the total weight.

Explanation of the Results

From the results, it is clear that the partial degradation products ofthe present invention are excellent in surface tension lowering propertyand emulsifying property, and particularly, many products of the presentinvention are more excellent in any of the various points in comparisonwith conventional sucrose fatty acid esters. And it is noted thatComparative test samples 6 to 8 are excellent in surface tensionlowering property, but are poor in emulsifying property.

Additional tests of emulsifying property of Test samples 1, 5 and 6using a smaller amount of the sample (concentration: 0.3% by weight)gave the value of emulsifying property which is greater than 24 hours.On the other hand, an additional test of the above property of thesucrose fatty acid ester in concentration of 0.3% and 0.15% by weightgave 30 minutes and less than 10 minutes of emulsion state maintainingtime, respectively.

TEST 3 Foaming Test

The values of foaming property of Test samples and Comparative testsamples prepared in Examples and Comparative examples, and a sucrosefatty acid ester (Comparative test sample 10) are determined byRossmiles test (JIS K-3362) in concentration of 0.3% using pure water asa solvent at 25° C. The results are shown in Table 6.

                                      TABLE 6                                     __________________________________________________________________________             Surface                                                                       tension (dyne/cm)                                                                         Emulsified                                                                             Foaming property (mm)                                    Addition of                                                                         Addition of                                                                         state maintain-                                                                        Immediately                                                                          5 minutes                                         0.1% of the                                                                         0.3% of the                                                                         ing time after  after                                             sample                                                                              sample                                                                              (min or hour)                                                                          foaming                                                                              foaming                                  __________________________________________________________________________    Comparative                                                                          1 59.7  58.0  <10 (mins)                                               test   2 61.0  57.2  <10 (mins)                                                                             8      6                                        sample 3 55.0  52.9  <10 (mins)                                                                             10     4                                               4 60.9  56.8  <10 (mins)                                                      5 67.5  61.5  <10 (mins)                                                                             15     7                                               6 32.5  31.0  <10 (mins)                                                      7 32.0  30.8  <10 (mins)                                                      8 48.7  46.0  <10 (mins)                                                      9 60.9  60.1  <10 (mins)                                                      10                                                                              34.5  34.2  8   hrs  34     31                                              11                                                                              63.5  62.7  <10 (mins)                                               Test   1 34.5  31.7  more than 24 hrs                                         sample 2 33.0  30.9  24  hrs                                                         3 31.0  29.8  8   hrs                                                         4 30.5  29.2  1   hrs                                                         5 34.8  33.8  more than 24 hrs                                                6 34.7  34.3  more than 24 hrs                                                                       <1     <1                                              7 30.8  30.3  5   hrs  1      <1                                              8 31.3  30.7  5   hrs  <1     <1                                              9 34.5  33.5  24  hrs                                                         10                                                                              31.1  30.6  20  mins 1      <1                                              11                                                                              34.7  31.9  more than 24 hrs                                                12                                                                              48.6  45.2  40  mins                                                        13                                                                              34.0  32.0  24  hrs  1      <1                                              14                                                                              34.9  33.1  more than 24 hrs                                                15                                                                              30.9  29.7  5   hrs  1      <1                                              16                                                                              31.3  30.1  more than 24 hrs                                                17                                                                              32.8  30.8  24  hrs  1      <1                                              18                                                                              31.2  30.4  5   hrs                                                         19                                                                              33.0  32.1  8   hrs  <1     <1                                              20                                                                              32.0  30.9  5   hrs                                                         21                                                                              34.4  33.9  12  hrs                                                         22                                                                              33.2  32.2  8   hrs                                                         23                                                                              34.2  32.9  10  hrs                                                  Blank    72.7        <10 (mins)                                               __________________________________________________________________________     *The blanks mean "not tested".                                           

Consideration of the Results

Test samples of the present invention are much lower in foaming propertyin comparison with the other samples. Surface active agents which arelower in foaming property so as to permit to facilitate rinsing havebeen desired as a detergent for laundering and washing foods ortableware. But surface active agents which fully satisfy the above andhave higher safety are not found yet. Test samples of the presentinvention can be efficiently used for these applications.

TEST 4

It is known that surface active agents give an influence on the behaviorof viscosity of starch suspension. An influence of the products of thepresent invention and other conventional surfactants upon gelatinizationof starch is tested by the following method.

One gram of Test sample of the present invention and 20 g of potatostarch (a reagent) were dispersed and dissolved in city water at 50° C.and the solution was diluted with city water at 50° C. into 500 ml. Theviscograph from BRABENDER Co., Ltd., was operated at 77 rpm using theabove solution as a sample under the following temperature changingcondition. The temperature of the sample was raised from 50° C. to 95°C. at the rate of 1.5° C./min., and was maintained at 95° C. for 45minutes. Then, the temperature was lowered to 50° C. at the rate of 1.5°C./min. During the change of temperature, the viscosity of the solutionwas recorded. The gelatinization initiating temperature and the highestviscosity of the solution are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                                     Gelatinization                                                                             The highest                                         Test sample  initiating   viscosity                                           No.          temperature (°C.)                                                                   (B.U.)                                              ______________________________________                                        Not added    66.0         720                                                 1            77.0         560                                                 7            86.0         480                                                 ______________________________________                                    

Consideration of the Results

The products of the present invention were recognized to have acharacteristic that they raise up the gelatinization initiatingtemperature of starch and reduce the viscosity at the time ofgelatinization. Accordingly, the products of the present invention canbe used as a softener or an aging inhibitor for bread.

TEST 5 Bread Baking Test

This test was carried out on the following samples, namely, Test samplesand Comparative test samples prepared in Examples and Comparativeexamples, sucrose fatty acid ester (Comparative test sample 10),palmitic acid monoglyceride of the trade name "Sunsoft" No. 8001 fromTaiyo Kagaku Co., Ltd., JAPAN (Comparative test sample 12), wheat glutenof a reagent from Wako Pure Chemical Co., Ltd., JAPAN (Comparative testsample 13), and the partial degradation product obtained by thefollowing method (Comparative test sample 14).

PREPARATION OF COMPARATIVE TEST SAMPLE 14

Twenty grams of the same wheat gluten as used in Examples 1 to 23 wasadded to 100 g of an aqueous solution containing 4 g of sodium sulfite.The mixture was heated at 30° C. for 60 minutes under stirring.Hydrochloric acid was added to obtain an aqueous solution of pH 1.5. Thegluten in the solution was treated with 0.2 g of pepsin and warmed at37° C. for 90 minutes under stirring. The resultant was neutralized bysodium hydroxide and diluted with pure water into a total weight of 200g, by which Comparative test sample 14 having an average molecularweight of 36,000 was obtained.

A. Baking Method

The following raw materials were baked using a bread baking device fromMatsushita Electric Industrial Co., Ltd., JAPAN and left at 25° C.

    ______________________________________                                        Bread baking device: National home bakery                                     SD-BT2 type                                                                   Material:                                                                     ______________________________________                                        Hard flour          280    g                                                  Sucrose             17     g                                                  Skimmed milk        6      g                                                  Common salt         5      g                                                  Butter              11     g                                                  Water               210    g                                                  Dried yeast         2.7    g                                                  Baking time         300    minutes                                            ______________________________________                                    

Each of Test samples of the present invention and Comparative testsamples was added to the materials by mixing and their concentrationshown in Table 8 is expressed as percentage by weight with respect tohard flour used.

B. Test Results

Volume, water content, its change with time, softness and degree ofretrogradation were observed. The breads used for the products of thepresent invention showed improvements on qualities which are equivalentor more in comparison with those used for Comparative test samples.

Typical examples of the breads added with the products of the presentinvention and Comparative test samples are shown in Table 8. ##EQU1##Softness (g/cm): This is expressed with tensile strength measured usingthe Rheometer (NRM-2010J.D-CW) from Fudo Kogyo Co., Ltd., JAPAN

Degree of retrogradation of starch (%): This is measured by the methodusing beta-amulase-Pullulanase [see K. Kainuma et al., J. Jap. Soc.Starch Soc. 28, No. 4, pp. 235 to 240 (1981)].

                                      TABLE 8                                     __________________________________________________________________________                         Test No.                                                                      1  2  3  4  5  6  7  8  9  10 11                                              Sample                                                                        no                                                                            addi-                                                                            Test sample                                                        Concentration                                                                         tion                                                                             1  4  6           13 16 19 17                         Evaluation   (% by weight)                                                                         0  0.5   0.05                                                                             0.3                                                                              0.5                                                                              3.0                                                                              0.5                                 __________________________________________________________________________    Evaluation                                                                          Volume --      2650                                                                             2940                                                                             2840                                                                             2870                                                                             3110                                                                             3140                                                                             3140                                                                             3070                                                                             3120                                                                             2840                                                                             2830                       items on                                                                            (cm.sup.3)                                                              test bread                                                                          Water  0       47.0                                                                             47.3                                                                             47.0                                                                             47.2                                                                             47.4                                                                             47.3                                                                             47.0                                                                             47.3                                                                             47.3                                                                             47.4                                                                             47.3                       and the                                                                             content (%)                                                             number of                                                                           Change of                                                                            2       1.9                                                                              1.4                                                                              1.3   1.3                                                                              1.2                                                                              1.0                                                                              1.3                                                                              1.4                                                                              1.5                                                                              1.6                        day after                                                                           water con-                                                                           3       2.8                                                                              1.7                                                                              1.6                                                                              2.2   1.6                                                                              1.3                                                                              1.5                                                                              1.7                                                                              1.9                                                                              2.0                        baking                                                                              tent with                                                                            4       3.6                                                                              2.5                                                                              2.2                                                                              3.1                                                                              2.6                                                                              2.4                                                                              1.8                                                                              2.0                                                                              2.5                                                                              2.8                                                                              2.8                              time (%)                                                                      Softness                                                                             0       9.5                                                                              4.9                                                                              5.2                                                                              7.0                                                                              5.0                                                                              4.8                                                                              5.1                                                                              4.9                                                                              4.7                                                                              6.2                                                                              6.4                              (g/cm) 2       16.7                                                                             10.2                                                                             8.1   9.6                                                                              8.4                                                                              8.0                                                                              7.7                                                                              9.6                                                                              11.5                                                                             12.3                                    3       19.9                                                                             14.4                                                                             10.3                                                                             18.6  11.2                                                                             10.0                                                                             10.1                                                                             14.2                                                                             16.4                                                                             16.7                                    4       30.1                                                                             20.5                                                                             14.7                                                                             27.0                                                                             17.3                                                                             16.0                                                                             13.2                                                                             13.4                                                                             20.4                                                                             21.3                                                                             21.4                             Degree of                                                                            0       27 15 17 23 16 12 10 13 14 18 16                               retrograda-                                                                          2       51 42 38       40    36 40 43 45                               tion of                                                                              3       60 47 42       44    40 45 48 50                               starch (%)                                                                           4       62 52 44       48    42 50 54 55                         __________________________________________________________________________                                        Test No.                                                                      12 13 14 15 16 17                                                             Sample                                                                        Comparative test sample                                               Concentration                                                                         13 6  4  14 10 12                                        Evaluation   (% by weight)                                                                         0.5                                       __________________________________________________________________________                   Evaluation                                                                          Volume --      2680                                                                             2640                                                                             2800                                                                             2700                                                                             2800                                                                             2870                                      items on                                                                            (cm.sup.3)                                                              test bread                                                                          Water  0       47.3                                                                             47.2                                                                             47.3                                                                             47.4                                                                             47.0                                                                             47.1                                      and the                                                                             content (%)                                                             number of                                                                           Change of                                                                            2       1.7                                                                              1.8                                                                              1.6                                                                              1.6                                                                              1.7                                                                              1.5                                       day after                                                                           water con-                                                                           3       2.8                                                                              2.6                                                                              2.3                                                                              2.2                                                                              2.1                                                                              2.0                                       baking                                                                              tent with                                                                            4       3.5                                                                              3.4                                                                              3.2                                                                              3.1                                                                              3.0                                                                              2.9                                             time (%)                                                                      Softness                                                                             0       9.7                                                                              7.7                                                                              7.2                                                                              8.7                                                                              7.0                                                                              6.5                                             (g/cm) 2       17.7                                                                             15.5                                                                             16.0                                                                             15.3                                                                             14.4                                                                             12.4                                                   3       21.5                                                                             18.8                                                                             17.8                                                                             16.8                                                                             17.1                                                                             16.7                                                   4       32.6                                                                             27.7                                                                             24.3                                                                             22.6                                                                             22.6                                                                             21.8                                            Degree of                                                                            0       27 24 22 19 20 18                                              retrograda-                                                                          2       51 49 47 46 48 46                                              tion of                                                                              3       59 57 54 54 57 51                                              starch (%)                                                                           4       63 60 57 56 61 54                         __________________________________________________________________________

Further the results of evaluation of the bread baked using Test samples1 and 13 of the present invention together with the sucrose fatty acidester or palmitic acid monoglyceride are shown in Table 9.

                                      TABLE 9                                     __________________________________________________________________________                         Test No.                                                                      18       19       20   21                                                     Sample                                                                        Test sample 1 +                                                                        Test sample 13 +                                                                       Test sample 1 +                                             sucrose fatty                                                                          palmitic acid                                                                          sucross fatty                                       Concentration                                                                         acid ester                                                                             monoglyceride                                                                          acid ester                             Evaluation   (% by weight)                                                                         0.25 + 0.25       0.1 + 0.4                                                                          0.4 + 0.1                         __________________________________________________________________________    Evaluation                                                                          Volume --      3340     3280     3060 3210                              items on                                                                            (cm.sup.3)                                                              test bread                                                                          Water  0       47.3     47.4     47.3 47.3                              and the                                                                             content (%)                                                             number of                                                                           Change of                                                                            2       1.0      0.9      1.3  1.2                               day after                                                                           water con-                                                                           3       1.4      1.3      1.6  1.5                               baking                                                                              tent with                                                                            4       2.0      1.8      2.3  2.2                                     time (%)                                                                      Softness                                                                             0       4.6      4.5      4.8  4.6                                     (g/cm) 2       7.7      7.5      10.0 8.3                                            3       12.1     10.0     13.7 12.6                                           4       15.0     13.3     18.5 15.4                                    Degree of                                                                            0       14       10       15   14                                      retrograda-                                                                          2       40       33       43   40                                      tion of                                                                              3       44       37       47   45                                      starch (%)                                                                           4       47       41       50   47                                __________________________________________________________________________

C. Consideration Bread Volume

As shown in Test 2 to 17 in Table 8, addition of 0.5% by weight of Testsamples of the present invention permits the bread volume to increase by7 to 18%, and the same addition as above of Comparative test samplespermits the bread volume to increase only by 0 to 8%. This clearly showsthe former is superior in bread volume to the latter.

Further, it can be seen from the results of Test Nos. 18 to 21 that theuse of sucrose fatty acid ester or palmitic acid monoglyceride togetherwith Test sample of the present invention permits of more increasing ofbread volume.

Water Retention and Softness

The bread baked using Test samples of the present invention is superiorin water retention to the control bread and the bread baked usingComparative test samples because change of water content with time ofthe former is smaller than that of the latter.

The former is also superior in softness to the latter.

Degree of Retrogradation of Starch

Such degree of the breads baked using Test samples of the presentinvention decreases in comparison with the ones baked using Comparativetest samples. The retrogradation of starch of the former is slower thanthat of the latter (about 1 or 2 days).

TEST 6 Noodle Making Test

Generally, noodles tend to slowly lower their qualities, such astexture, palatability or untangling property. Accordingly, Test samplesof the present invention were compared with Comparative test samples,which are the same as used in Test 5.

A. Preparation of Noodles

Medium flour 100 g, common salt 2 g, water 35 g and a predeterminedamount of a Test sample were kneaded to obtain noodle dough. A strip ofthe dough of about 1.2 mm in thickness was made by pressing andspreading it with a rod. The strip was cut with No. 20 angle cutter toobtain long noodles. The long noodles were cut to about 30 cm long andthe resultant was boiled in water for about 5 minutes and stored in arefrigerator at about 5° C.

The noodles were dipped in boiled water for about 1 minute withoutstirring and observed their readiness for untangling. Organoleptic testresults are shown in Table 10.

B. Test Results

The noodles made using Test samples 1 to 23 were superior in untanglingproperty and palatability to those made using Comparative test samples.The results of the organoleptic test in which 10 panelists participateare shown in Table 10, wherein concentration (%) shows percentage byweight of the samples with respect to wheat flour.

                                      TABLE 10                                    __________________________________________________________________________                    Storage day number                                                            1         3         5                                                 Concentration                                                                         Untangling                                                                          Palata-                                                                           Untangling                                                                          Palata-                                                                           Untangling                                                                          Palata-                             Sample  (%)     property                                                                            bility                                                                            property                                                                            bility                                                                            property                                                                            bility                              __________________________________________________________________________    Test sample 6                                                                         0.5     ++    ◯                                                                     ++    ◯                                                                     ±  ◯                       Test sample 13                                                                        0.2     +     ◯                                                                     ±  ◯                                                                     -     Δ                                     0.5     ++    ◯                                                                     ++    ◯                                                                     +     ◯                               1.0     ++    ◯                                                                     ++    ◯                                                                     +     ◯                       Test sample 19                                                                        0.5     ++    ◯                                                                     +     ◯                                                                     ±  Δ                             Comparative                                                                           0.5     ±  Δ                                                                           -     x   -     x                                   Test sample 13                                                                Comparative                                                                           0.5     +     Δ                                                                           ±  Δ                                                                           -     x                                   Test sample 6                                                                 Comparative                                                                           0.5     +     Δ                                                                           +     Δ                                                                           ±  x                                   Test sample 14                                                                __________________________________________________________________________     Evaluation of untangling property)                                            ++: much better than the control                                              +: better than the control                                                    ±: slightly better than the control                                        -: equivalent to the control                                                  (Evaluation of palatability)                                                  ◯: much better than the control                                   Δ: slightly better than the control                                     x: equivalent to the control                                             

TEST 7 Stabilization Test on Dressings

A dressing like food consisting of salad oil, water, sucrose and commonsalt was prepared.

The effect of the following samples to stabilize the dressing like foodwas measured, i.e., Test samples of the present invention andComparative test samples prepared by Comparative examples, sucrose fattyacid ester (Comparative test sample 10), palmitic acid monoglyceride(Comparative test sample 12) and wheat gluten (Comparative test sample13).

Test Method

To 50 ml of city water containing a predetermined amount of the sampleare added 12.5 g of sucrose and 3.5 g of common salt and the mixture isstirred to obtain a solution. Eighty ml of a salad oil are added to thesolution and the resultant is stirred and mixed for 5 minutes with ahomomixer. Thereafter, 12 ml of vinegar are added and the resultant isstirred and mixed for 1 minute to obtain a dressing like food.

The effect of Test sample to stabilize such dressing like food wasevaluated with the time required for separation of the food into a waterphase and an oil phase.

Test results are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                                        Concentration                                                                 (% by weight                                                                              Evaluation of                                                     to the total                                                                              stabilizing                                       Sample          weight)     effect                                            ______________________________________                                        Example                                                                       Test sample 1    0.05       ◯                                                     0.1         ⊚                                                  0.5         ⊚                                  Test sample 3   0.5         ⊚                                  Test sample 6   0.1         ◯                                                     0.5         ⊚                                  Test sample 12  0.5         ⊚                                  Test sample 14  0.1         ◯                                                     0.5         ⊚                                  Test sample 16  0.5         ⊚                                  Test sample 17  0.5         ⊚                                  Test sample 19  0.5         ◯                                     Test sample 21  0.5         ◯                                     Comparative example                                                           Comparative     0.5         XX                                                test sample 13                                                                Comparative     0.5         X                                                 test sample 6                                                                 Comparative     0.5         X                                                 test sample 3                                                                 Comparative     0.5         Δ                                           test sample 4                                                                 Comparative     0.5         ◯                                     test sample 10                                                                Comparative     0.5         Δ                                           test sample 12                                                                not added       0           XX                                                Example                                                                       Test sample 1   0.01 + 0.04 ◯                                       +             0.02 + 0.08 ⊚                                  Comparative     0.025 + 0.025                                                                             ⊚                                  test sample 10  0.04 + 0.01 ◯                                     (sucrose fatty  0.08 + 0.02 ⊚                                  acid ester)                                                                   ______________________________________                                    

The meanings of the symbols expressing the stabilizing effect in Table11 are as follows.

⊚ . . . Stable for more than 72 hours

◯ . . . Separating into two phases during 30 minutes to 72 hours

Δ . . . Separating into two phases during 30 minutes to 24 hours

× . . . Separating into two phases within 30 minutes

× . . . Separating immediately

Consideration

As seen from the data in Table 11, the stabilizing effect of Testsamples of the present invention is superior to that of Comparative testsamples. The use of Test sample with sucrose fatty acid ester is alsouseful in improving the stabilizing effect and it shows a synergisticeffect.

TEST 8 Test on Stabilization of Margarine

A margarine like emulsion of water in oil type was prepared by usingsoya bean oil, hardened fish oil and hardened palm oil.

The effect of Test samples to stabilize the above emulsion was measured.

Test Method

A predetermined amount of a Test sample and 80 g of fatty oil were putinto a mixing vessel. The mixture was heated to about 90° C. to form auniform solution or dispersion. Thus an oil phase was prepared. Sixteengrams of water were added to the oil phase and the resultant was stirredand cooled to obtain a uniform emulsion of water in oil type. Thecomposition of fatty oils are as follows.

    ______________________________________                                        Oil                  % by weight                                              ______________________________________                                        Soya bean oil        26                                                       Hardened fish oil (m.p. 30° C.)                                                             68                                                       Hardened palm oil (m.p. 45° C.)                                                              6                                                       Total                100                                                      ______________________________________                                    

The stabilizing effect to the obtained water in oil type emulsified oilcomposition was evaluated by storing the composition at 25° C. or 35° C.for five days and observing coarseness and separating state of the oilphase and the water phase of the composition when it melts orintermediately melts.

The samples other than Comparative test samples 10 and 12 were desaltedby ultrafiltration and spray-dried. The obtained powder was used for thetest. Comparative test samples 10 and 12 in the form of powder were usedas such.

Test Results

They are shown in Table 12.

                  TABLE 12                                                        ______________________________________                                                                           Separating                                                        Coarseness  state after                                                       after keeping                                                                             keeping at                                 Sample       Additon (g)                                                                             at 25° C.                                                                          35° C.                              ______________________________________                                        Example                                                                       Test sample 1                                                                              0.1       Slightly coarse                                                                           Δ                                                 0.3       Smooth      ⊚                                        1.0         "         ⊚                                        3.0         "         ⊚                           Test sample 3                                                                              1.0         "         ⊚                           Test sample 5                                                                              1.0         "         ⊚                           Test sample 12                                                                             1.0         "         ⊚                           Test sample 13                                                                             1.0         "         ⊚                           Test sample 16                                                                             1.0         "         ⊚                           Test sample 17                                                                             1.0         "         ⊚                           Test sample 19                                                                             0.3       Slightly coarse                                                                           Δ                                                 1.0       Smooth      ◯                              Test sample 23                                                                             1.0         "         ◯                              Comparative example                                                           Comparative  1.0       Containing  X                                          test sample 13         some particles                                         Comparative  1.0       Slightly sepa-                                                                            X                                          test sample 6          rating and                                                                    coarse                                                 Comparative  1.0       Coarse      Δ                                    test sample 3                                                                 Comparative  1.0       Containing a                                                                              Δ                                    test sample 4          few particles                                          Comparative  1.0       Smooth      Δ                                    test sample 10                                                                Comparative  1.0         "         ◯                              test sample 12                                                                Not added    0         Containing  X                                                                 some particles                                         Example                                                                       Test sample 1                                                                              0.08 + 0.22                                                                             Smooth      ⊚                             +          0.05 + 0.05                                                                               "         ⊚                           Comparative  0.15 + 0.15                                                                               "         ⊚                           test sample 12                                                                             0.22 + 0.08                                                                               "         ⊚                           (Palmitic acid                                                                monoglyceride)                                                                ______________________________________                                    

The meanings of the symbols expressing the separating state in Table 12are as follows.

⊚: Emulsified uniformly

◯: Having slight color shading

Δ: Separating a little

×: Separating completely

Consideration

As seen from the data in Table 12, Test samples of the present inventionserve to make finer the water phase and the oil phase of margarine andprevent margarine from separation when it melts. Generally, Test samplesare superior in such effect to Comparative test samples. The combinationuse of the test sample with palmitic acid monoglyceride shows asynergistic effect.

TEST 9 Improving Effect on the Quality of Kamaboko (A Boiled Fish Paste)A. Test Method and Condition

The mixture having the composition mentioned below was ground down toobtain ground fish for kamaboko. This ground fish was divided to someportions and the different Test samples were added to each of theportions. The mixtures were kneaded. After measurement of hardness ofthe finished ground fish, it was packed into a polyvinylidene chloridetube (width of the folded tube: 4.5 cm). The resultant was left for 15hours at 15° C. and heated to 90° C. for 40 minutes to obtain a kamabokopacked in a tube. The breaking strength and the breaking strain of theobtained kamaboko were measured. The hardness of ground fish relates toits formability, and the breaking strength and the breaking strain ofthe product represent its texture.

    ______________________________________                                        (Composition of kamaboko)                                                     ______________________________________                                        Frozen ground fish of pollack                                                                       2 Kg   (100 parts                                                                    of weight)                                       Common salt           44 g   (2.2 parts                                                                    of weight)                                       Sucrose               18 g   (0.9 parts                                                                    of weight)                                       Sodium glutamate      10 g   (0.5 parts                                                                    of weight)                                       Mirin (Japanese flavoring spirit)                                                                   10 g   (0.5 parts                                                                    of weight)                                       Potato starch         140 g  (7 parts of                                                                   weight)                                          ______________________________________                                    

Hardness of Ground Fish

Ground fish obtained was packed in a glass vessel of 6 cm in diameterand 5 cm in height to prepare a test sample. When the sample wascompressed to the height of 45 mm using the Rheometer (NRM-2010J.D-CW)from Fudo Kogyo Co., Ltd., JAPAN, its stress was measured. The value isdefined as hardness of ground fish.

Breaking Strength and Breaking Strain of Kamaboko

The obtained kamaboko was cut to 3 cm in height and pressed using thesame Rheometer as used above to measure the breaking strength (stress(g) when breaking) and the breaking strain (mm).

B. Test Results

The results are shown in Table 13.

                                      TABLE 13                                    __________________________________________________________________________                                 Breaking                                                                           Breaking                                                    Concentration                                                                         Hardness                                                                           strength                                                                           strain                                      Sample          (wt %)  (g)  (g)  (mm)                                        __________________________________________________________________________    Example                                                                              Test sample 1                                                                          1       916  1704 21.1                                               Test sample 2                                                                          0.2     836  1536 20.0                                                        0.5     894  1802 21.7                                                        1       923  1905 22.2                                                        4       1012 2060 23.9                                               Test sample 6                                                                          1       920  1920 22.6                                               Test sample 13   892  1902 22.1                                               Test sample 16   898  1910 23.2                                               Test sample 17   888  1904 22.0                                               Test sample 19   859  1648 20.5                                        Comparative                                                                          Comparative                                                                            1       785  1506 18.0                                        example                                                                              test sample 13                                                                Comparative      822  1564 18.4                                               test sample 6                                                                 Comparative      830  1536 18.6                                               test sample 3                                                                 Comparative      818  1524 18.5                                               test sample 4                                                                 Comparative      834  1572 18.8                                               test sample 10                                                                Comparative      821  1524 18.5                                               test sample 12                                                         Not added       0       807  1486 18.0                                        Example                                                                              Test sample 2 +                                                                        0.8 + 9.2                                                                             978  1935 23.0                                               Comparative                                                                            0.5 +  0.5                                                                            995  1988 23.6                                               test sample 10                                                                         0.2 + 0.8                                                                             920  1897 22.1                                               (sucrose fatty                                                                acid ester)                                                                   Test sample 2 +                                                                        0.8 + 0.2                                                                             971  1925 22.7                                               Comparative                                                                            0.5 + 0.5                                                                             989  1976 23.2                                               test sample 12                                                                         0.2 + 0.8                                                                             913  1892 20.6                                               (palmitic-acid                                                                monoglyceride)                                                         __________________________________________________________________________     Note: Comparative test samples used are the same ones as used in Test 7. 

As shown in Table 13, rigidness of kamaboko can be remarkably improvedby Test samples of the present invention.

Further, the combined use of Test sample of the present invention andsucrose fatty acid ester, palmitic acid monoglyceride or the like showsa synergistic effect in improving the quality of protein foods.

TEST 10

This test was conducted in the same manner as in Test 9 by replacing 300g in 2 Kg of the frozen ground fish of pollack, which is one ingredientof the kamaboko used in the Test 9, with 300 g of wheat gluten, and theimproving effect of Test samples of the present invention on the qualityof the kamaboko was evaluated. The results are shown in Table 14.

                                      TABLE 14                                    __________________________________________________________________________                                Breaking                                                                           Breaking                                                    Concentration                                                                         Hardness                                                                           strength                                                                           strain                                       Sample         (wt %)  (g)  (g)  (mm)                                         __________________________________________________________________________    Comparative                                                                          Not added                                                                             1       772  1562 18.3                                         example                                                                       Example                                                                              Test sample 2                                                                         1       853  1961 22.3                                                Test sample 6                                                                         1       874  1970 22.7                                                Test sample 16                                                                        1       830  1912 23.0                                         __________________________________________________________________________

TEST 11 Improving Effect on the Quality of Hamburger

Each of the test samples of the present invention was added to hamburgermaterials having the below composition containing wheat gluten.

    ______________________________________                                        (Hamburger materials)                                                         ______________________________________                                        Minced pork           22.5   parts                                            Common salt           1.0    parts                                            Minced beef           22.5   parts                                            Minced fat pork       10.0   parts                                            Onion                 23.4   parts                                            Bread crumb           6.4    parts                                            Wheat gluten          10.0   parts                                            Sodium glutamate      0.3    parts                                            White pepper          0.1    parts                                            Nutmeg                0.2    parts                                            Water                 4.0    parts                                            ______________________________________                                    

                                      TABLE 15                                    __________________________________________________________________________                   Addition                                                                           Compati-                                                  Sample         (part)                                                                             bility                                                                             Texture                                                                            Flavor                                          __________________________________________________________________________    Comparative                                                                          Not added                                                                             0    Bad  Bad  Inferior                                        example                                                                       Example                                                                              Test example 6                                                                        1    Good Good Equivalent                                             Test example 13                                                                       1    Good Good Equivalent                                             Test example 17                                                                       1    Good Good Equivalent                                      __________________________________________________________________________

This test was conducted employing ten panelists and the results weresummarized in Table 15.

The texture and the flavor were evaluated in comparison with thestandard hamburger prepared using the same material as mentioned abovewithout wheat gluten.

From the above results, test samples of the present invention improvethe palatability and flavor of hamburger.

TEST 12 Improving Effect on the Quality of Soya Bean Protein Material

Soya bean protein powder (Fujipro R from Fuji Seiyu Co., Ltd., JAPAN)was dissolved in water to obtain a 8% aqueous solution of it. Thepredetermined amount of each of Test samples of the present inventionand Comparative test samples was added to the solution and the mixturewas mixed with stirring and spray-dried to obtain a powder product.

The obtained powder was hermetically sealed in a polyethylene tube. Itwas kept at 25° C. and then the time course of its solubility (NSI:Nitrogen Solubility Index) was determined.

The results are shown in Table 16.

                                      TABLE 16                                    __________________________________________________________________________                            Solubility (NS1 %)                                                    Concentration                                                                         Time                                                  Sample          (wt %)  0 2 months                                                                           5 months                                                                           10 months                                 __________________________________________________________________________    Example                                                                              Test sample 2                                                                          0.2     98                                                                              91   80   63                                                        0.5     98                                                                              94   87   75                                                        1       98                                                                              96   90   85                                                        3       99                                                                              97   93   88                                               Test sample 4                                                                          1       98                                                                              91   84   73                                               Test sample 6    98                                                                              96   89   84                                               Test sample 7    98                                                                              95   88   83                                               Test sample 14   99                                                                              95   89   82                                               Test sample 15   98                                                                              94   86   80                                               Test sample 18   98                                                                              95   87   82                                               Test sample 21   99                                                                              92   85   77                                               Test sample 22   99                                                                              92   84   74                                               Test sample 23   98                                                                              91   84   73                                        Comparative                                                                          Comparative                                                                            1       98                                                                              90   76   58                                        example                                                                              test sample 13                                                                Comparative      98                                                                              91   79   60                                               test sample 6                                                                 Comparative      98                                                                              90   78   59                                               test sample 3                                                                 Comparative      99                                                                              91   78   60                                               test sample 4                                                                 Comparative      98                                                                              91   83   72                                               test sample 10                                                                Comparative      98                                                                              91   81   67                                               test sample 12                                                         Not added       0       98                                                                              90   75   57                                        Example                                                                              Test sample 2 +                                                                        0.8 + 0.2                                                                             98                                                                              97   92   87                                               Comparative                                                                            0.5 + 0.5                                                                             99                                                                              97   94   91                                               test sample 10                                                                         0.2 + 0.8                                                                             99                                                                              94   88   80                                               Test sample 2 +                                                                        0.8 + 0.2                                                                             98                                                                              96   91   86                                               Comparative                                                                            0.5 + 0.5                                                                             98                                                                              96   93   89                                               test sample 12                                                                         0.2 + 0.8                                                                             98                                                                              93   87   78                                        __________________________________________________________________________     Note: Comparative test samples used are the same ones as used in Test 7. 

As described above, it was determined that Test samples of the presentinvention prevented the reduction of solubility of the soya bean proteinand stably kept its quality, for example depressing its shrinkage whenheated.

Further, it can be seen that the use of Test samples of the presentinvention, and a combined use of Test sample 2 and sucrose fatty acidester (Comparative test sample 10) or palmitic acid monoglyceride(Comparative test sample 12) permits more improvement of the abovestabilizing effect.

The above soya bean protein or wheat gluten have been used as a bulkingagent for meat balls and hamburgers, and is said also that its additionto foods softens the palatability. But sufficient mixing of the mixtureis very difficult when the material is added to minced meat foods, whichcomes into a problem in the art.

Further, it was confirmed that each of Test samples 2 and 14, and acombination of Test sample 2 and Comparative test sample 10 in the formof powder which are shown in Table 16 could be easily mixed with othermaterials and also easily homogenized, as a bulking agent. Thus, Testsamples of the present invention are very useful as a quality-improvingagent for soya bean protein materials.

TEST 13 Improving Effect on the Quality of Tofu (Bean Curd)

One hundred grams of soya bean were washed with water and water at about10° C. is added to the soya bean into a total weight of about 250 g,which is left at about 10° C. 15 hours. After addition of 250 g ofwater, the soya bean was ground, added with Test sample and boiled.After 5 minutes, the height of its foaming was measured, and boiled for10 minutes. Boiling water was added to make a total weight of 1000 g.The resultant mixture was filtered to separate into soya bean milk andtofu refuse. The tofu milk cooled to 75° C. and it was flocculated byaddition of 3 g of calcium sulfate in 30 ml of water at 40° C. After 10minutes, a tofu product was obtained by pressing.

The height of foaming in above boiling, the yield in weight and thequality (elasticity and solid content) of the obtained tofu are shown inTable 17.

                                      TABLE 17                                    __________________________________________________________________________                    Concen-                                                                            Height                                                                             Weight   Solid                                                      tration                                                                            of foam                                                                            of tofu                                                                           Elas-                                                                              content                                    Sample          (wt %)                                                                             (cm) (g) ticity                                                                             (%)                                        __________________________________________________________________________    Example                                                                              Test sample 3                                                                          1    10   1780                                                                              Stronger                                                                           11.4                                              Test sample 7                                                                          0.2  50   1540                                                                              Stronger                                                                           12.2                                              Test sample 7                                                                          0.5  25   1670                                                                              Stronger                                                                           11.9                                              Test sample 7                                                                          1    9    1750                                                                              Stronger                                                                           11.6                                              Test sample 15                                                                         1    18   1720                                                                              Stronger                                                                           11.8                                              Test sample 7 +                                                                        0.8 + 0.2                                                                          8    1760                                                                              Stronger                                                                           11.6                                              Comparative                                                                   test sample 12                                                                Test sample 7 +                                                                        0.5 + 0.5                                                                          6    1780                                                                              Stronger                                                                           11.5                                              Comparative                                                                   test sample 12                                                                Test sample 7 +                                                                        0.2 + 0.8                                                                          15   1640                                                                              Stronger                                                                           12.0                                              Comparative                                                                   test sample 12                                                         Not added       0    >100 1500                                                                              Ordinary                                                                           12.4                                       Comparative                                                                          Comparative                                                                            1    20   1610                                                                              Slightly                                                                           12.1                                       example                                                                              test sample 12         Stronger                                        __________________________________________________________________________     Note: Comparative test sample 12 is the same one as used in Test 7.      

It can be seen from the above results that Test samples of the presentinvention improve the elasticity and the yield in weight of tofu andprevent troublesome foaming, and further such effect is synergisticallyincreased by the combination use of Test sample of the present inventionand palmitic acid monoglyceride.

TEST 14 Improving Effect on the Quality of Coffee Whitener

One to three grams of Test sample of the present invention and 30 g ofthe skimmed milk powder (from Snow Brand Milk Products Co., Ltd., JAPAN)were dispersed or dissolved in hot water at 65° C. to make a totalweight of 700 g. The resultant liquid was slowly added with stirring tohardened soya bean oil (raising of melting point, 36° C.) at 70° C.wherein 0.1 g of palmitic acid monoglyceride is dissolved. The mixturewas stirred at 70° C. for 10 minutes and homogenized at a pressure of 50Kg/cm² using a high pressure homogenizer to obtain a coffee whitener.

This coffee whitener was tested by the following method.

Test Method

Thirteen grams of roasted Brazilian coffee beans were extracted with 100ml of hot water at 85° C. The obtained coffee liquid was maintained at80° C. and 10 ml of the above coffee whitener were added. After stirringthe degree of feathering (a phenomenon that feather like flocculates ofcoffee cream or whitener float on the surface of coffee liquid) wasdetermined with the ranks of (+) "feathering occurs", (±) "slightfeathering" and (-) "no feathering" and also the time required to form afilm of coffee whitener was determined.

Test Results

No feathering occurs in the above test of Test samples 1 to 23 of thepresent invention, and it took more than 10 minutes for all the abovesamples to form their film. The test results of the typical Test samplestogether with some Comparative test samples are shown in Table 18.

                  TABLE 18                                                        ______________________________________                                                                           Time                                                                          required to                                                  Addition Feath-  form film                                  Sample            (g)      ering   (minute)                                   ______________________________________                                        Example  Test sample 1                                                                              3        (-)   ≧30                                        Test sample 4                                                                              3        (-)   17                                                Test sample 6                                                                              3        (-)   ≧30                                        Test sample 7                                                                              3        (-)   ≧30                                        Test sample 7                                                                              2        (-)   22                                                Test sample 7                                                                              1        (±)                                                                              9                                                 Test sample 13                                                                             3        (-)   24                                                Test sample 16                                                                             3        (-)   ≧30                                        Test sample 18                                                                             3        (-)   ≧30                                        Test sample 19                                                                             3        (-)   16                                                Test sample 21                                                                             3        (-)   15                                                Test sample 22                                                                             3        (-)   15                                                Test sample 23                                                                             3        (-)   11                                       Not added         0        (+)     2                                          Comparative                                                                            Comparative  3        (+)   2                                        example  test sample 13                                                                Comparative  3        (+)   5                                                 test sample 6                                                                 Comparative  3        (±)                                                                              7                                                 test sample 3                                                                 Comparative  3        (+)   3                                                 test sample 4                                                                 Comparative  3        (± )                                                                             8                                                 test sample 10                                                                Comparative  3        (±)                                                                              4                                                 test sample 12                                                       Example  Test example 7 +                                                                           1.6 + 0.4                                                                              (-)   ≧30                                        Comparative  1 + 1    (-)   ≧30                                        test sample 10                                                                             0.4 + 1.6                                                                              (-)   20                                       ______________________________________                                         Note: Comparative test samples used are the same ones as used in Test 7. 

It can be seen from the above results that when the Test sample of thepresent invention is used in coffee whitener, feathering and filmformation are sufficiently prevented and also such effect issynergistically increased by use of a combination of Test sample andComparative test sample.

TEST 15 Improving Effect on the Quality of Whipping Cream

Forty five parts of hardened soya bean oil (raising of melting point,36° C.) and Test sample of the present invention or Comparative testsample were added to 65 parts of whole milk, and the mixture was stirredat 70° C. for 15 minutes by use of a homomixer, homogenized at 80 Kg/cm²using a homogenizer. The emulsified state of the resultant was observed.The emulsion was sterilized by heating at 70° C. for 10 minutes, rapidlycooled to 10° C. and aged at 5° C. for 12 hours in a refrigerator toobtain a cream like oil composition. This composition was stirred at 600rpm using an electric hand whipper to obtain a whipping cream.

The whipping cream was tested on the following properties.

Evaluation Items and Test Methods

(1) Viscosity: Rion BO-2 type viscometer was used.

(2) Overrunning: (Percent increase in maximum foaming ##EQU2## (3)Foaming time: The time required for the initial composition to reach tothe maximum foaming condition by whipping at 600 rpm using an electrichand whipper.

(4) Duration of the maximum foaming: The time for which the whippingcream can keep its most suitable foaming condition when the cream iswhipped in the same manner as in the above (3).

(5) Shape retaining property and surface texture:

A . . . good

AB . . . slightly better

B . . . no good (unpractical)

Test Results

The above tests were conducted on Test samples 1 to 23 of the presentinvention and Comparative test samples. The results of the typicalsamples are shown in Table 19. The result of the combined use of Testsample 7 and sucrose fatty acid ester (Comparative test sample 10) isalso shown in Table 19.

                                      TABLE 19                                    __________________________________________________________________________                    Concentra-                                                                    tion (% by              Foaming     Shape                                     weight with                                                                           Emulsified                                                                          Viscosity                                                                          Over-                                                                              time.sup.(3)                                                                        Duration of                                                                         retaining                                                                           Surface             Sample          respect to oil)                                                                       state (CP).sup.(1)                                                                       running.sup.(2)                                                                    (min/sec.)                                                                          foaming.sup.(4)                                                                     property.sup.(5)                                                                    texture.sup.(6)     __________________________________________________________________________    Example                                                                              Test sample 1                                                                          1.0     A     150  120  4/10  40 sec                                                                              A     A                          Test sample 4                                                                          1.0     A     120  100  5/20  40    A     A                          Test sample 6                                                                          1.0     A     120  120  5/40  45    A     A                          Test sample 7                                                                          1.0     A     110  130  4/20  35    A     A                          Test sample 7                                                                          0.5     AB    180  120  3/50  25    A     A                          Test sample 7                                                                          0.3     AB    350  100  5/10  20    AB    AB                         Test sample 14                                                                         1.0     A     140  140  4/10  40    A     A                          Test sample 15                                                                         1.0     A     120  120  5/20  45    A     A                          Test sample 17                                                                         1.0     A     150  130  6/40  30    A     A                          Test sample 19                                                                         1.0     A     140  135  6/10  40    A     A                          Test sample 21                                                                         1.0     A     170  120  5/50  35    A     A                          Test sample 23                                                                         1.0     AB    220  80   5/40  25    A     AB                  Not added       0       B     --   55   3/20  5     B     B                   Comparative                                                                          Comparative                                                                            10      B     800  40   7/20  5     B     B                   example                                                                              test sample 13                                                                Comparative                                                                            10      B     290  60   7/10  5     B     B                          test sample 6                                                                 Comparative                                                                            10      B     240  65   6/00  15    B     AB                         test sample 3                                                                 Comparative                                                                            10      AB    150  95   4/30  5     B     AB                         test sample 10                                                                Comparative                                                                            10      AB    160  150  5/20  10    AB    AB                         test sample 12                                                         Example                                                                              Test sample 1 +                                                                        0.4 - 0.1                                                                             A     120  130  5/20  55    A     A                          Comparative                                                                            0.25 - 0.25                                                                           A     110  130  5/00  70    A     A                          test sample 10                                                                         0.1 - 0.4                                                                             A     130  120  6/10  60    A     A                   __________________________________________________________________________     Note: Comparative test samples used are the same ones as used in Test 7. 

TEST 16 Test of Washing for Removing Dirt which Adheres to Tablewares orthe Like, Based on JIS K-3370 1. Test Method and Condition

(i) Preparation of a Model of Dirty Pieces

a Twenty grams of a mixture of tallow and soya bean oil (1:1), 2.5 g ofmonoolein and 1 g of Oil Red (Sudan III) were dissolved in 600 ml ofchloroform to prepare a bath of stain.

b One set of six slide glasses was dipped in the stain bath by thelength of about 55 mm of these glasses for 1 to 2 seconds and was slowlytaken out of the bath.

c The slide glasses to which the stain adheres were air-dried, andsubjected to a washing test in a room at a constant temperature andhumidity (25° C., 40% RH), according to the following procedure.

(ii) Method of Washing Test

In a modified Leenerts type detergency tester the six stain adheredslide glasses were settled. Test water and a Test sample (a detergent)were added into the tester and it was operated to wash the glasses for 3minutes. The glasses were then rinsed by test water for 1 minute andair-dried. The detergency of Test sample is evaluated.

The composition of test water and test conditions are as follows.

Test water: An aqueous solution obtained by dissolving calcium chloride(dihydrate, 59.0 mg/l) and magnesium chloride (hexahydrate, 27.2 mg/l)in distilled water

Amount of water: 700 ml

Temperature of water: 30°±1° C. (both of washing water and rinsingwater)

Rate of revolution of the tester: 250±10 rpm

(iii) Method of Evaluation of the Detergency of the Samples

The slide glasses air-dried were washed with ethyl acetate to dissolvethe stain, which are made up to a total volume of 100 ml. The absorbanceof the obtained ethyl acetate washing was determined at the wave lengthof 500 nm and then the washing rate of the sample is calculated usingthe following equation. ##EQU3##

2. Test Results

(i) Test samples 1 to 23 of the present invention and Comparative testsamples prepared in Examples were subjected to the above washing testand all of washing rates of the test is 70% or more and higher than thevalue of the control without addition (washing rate 29%). The typicaltest results of Test samples are shown in Table 20 with those ofComparative test samples.

                  TABLE 20                                                        ______________________________________                                                   Molecular  Concentration                                                                              Washing                                    Sample     weight     (g/l)        rate (%)                                   ______________________________________                                        Test sample 3                                                                            16500      0.25         75                                         Test sample 4                                                                             980       0.25         72                                         Test sample 6                                                                            22000      0.25         72                                         Test sample 7                                                                            15000      0.25         78                                         Test sample 7                                                                            15000      0.1          60                                         Test sample 7                                                                            15000      0.05         37                                         Test sample 10                                                                            670       0.25         71                                         Test sample 13                                                                           11800      0.25         78                                         Test sample 22                                                                           24500      0.25         67                                         Not added  --         --           29                                         Comparative                                                                              --         0.25         33                                         test sample 13                                                                Comparative                                                                              --         0.25         60                                         test sample 10                                                                Comparative                                                                              --         0.1          46                                         test sample 10                                                                Comparative                                                                              --         0.05         30                                         test sample 10                                                                Comparative                                                                              --         0.25         34                                         test sample 12                                                                ______________________________________                                    

(ii) A sample of a combination of Test sample 7 and Comparative testsample 10 (sucrose fatty acid ester) was tested in the same manner as inthe above (i) and the test results are shown in Table 21.

                  TABLE 21                                                        ______________________________________                                                              Concentration                                                                             Washing rate                                Sample     Weight ratio                                                                             (g/l)       (%)                                         ______________________________________                                        Combination of                                                                           1:4        0.1         62                                          Test sample 7                                                                            1:1        0.1         74                                          and Compara-                                                                             4:1        0.1         70                                          tive test                                                                     sample 10                                                                     ______________________________________                                    

(iii) Test sample 7, sodium dodecyl benzene sulfonate (DBS) and theircombination were tested in the same manner as in the above (i) exceptfor the use of a test water obtained by dissolving calcium chloride(dihydrate, 176 mg/l) and magnesium chloride (hexahydrate, 81.6 mg/l) indistilled water. The test results are shown in Table 22.

                  TABLE 22                                                        ______________________________________                                                        Concentration                                                                             Washing rate                                      Sample          (g/l)       (%)                                               ______________________________________                                        Test sample 7   0.25        67                                                DBS             0.25        25                                                Test sample 7 + DBS                                                                           0.175 + 0.125                                                                             82                                                                0.20 + 0.05 79                                                                0.05 + 0.20 68                                                ______________________________________                                         Note: Comparative test samples in Tables 20 to 22 are the same ones as        used in Test 7.                                                          

As seen from the above results, when a water of high hardness is used asa test water, the value of the washing rate of DBS which is an anionsurface active agent is decreased, but when DBS is used together withTest sample 7, an excellent washing rate is observed.

It can be seen from the above results that the combined use has aremarkable synergistic effect.

(iv) A mixture of 1 part of the powder sample obtained by air-dryingTest sample 7 and 4 parts of powdered soap was tested in the same manneras in the above (iii). It showed an excellent detergency and alsoinsolubilization of the powder soap did not take place. On the otherhand, when only the powdered soap was used, it was remarkablyinsolubilized, so that washing was impossible.

TEST 17 Drying and Finishing Effect After Washing

Thirty six transparent glass cups were dipped in commercially availablemilk, taken out of the milk and left for 30 minutes at room temperature.They were put into a rack and washed by 0.15% solution of a commerciallyavailable alkaline detergent at 60° C. for 4 minutes using the automaticwasher MRK-NEWAMATIC JET WASHER LABO-200 from Mitamura Riken Kogyo Co.,Ltd., JAPAN. Further the cups are rinsed by spraying on to them for 15seconds a rinsing water which is an aqueous solution of followingrinsing agents at 85° C. Immediately after rinsing, the cups were takenout of the washer, and the wetting state of their surface, the timerequired to dry them and the cleanness after drying were checked.

Composition of Rinsing Agents

    ______________________________________                                        Example (No. 1)                                                               Test sample 7         80%    by weight                                        Propylene glycol      20%    by weight                                        Comparative test example (No. 2)                                              Comparative test sample 10                                                                          8%     by weight                                        Proylene glycol       20%    by weight                                        City water            72%    by weight                                        ______________________________________                                    

The results are shown in Table 23.

                                      TABLE 23                                    __________________________________________________________________________                 Concentration                                                    Rinsing      (Effective   Time                                                agent        amount) Wetting                                                                            required                                            No. Sample used                                                                            (ppm)   state                                                                              to dry                                                                              Cleanness                                     __________________________________________________________________________    1   Test sample 7                                                                          50      ◯                                                                      2 to 3                                                                              ◯                                                           minutes                                             2   Comparative test                                                                       50      Δ                                                                            3 to 5                                                                              Δ                                           sample 10             minutes                                             City water only                                                                            x       x    More than                                                                           x                                                                       5 minutes                                           __________________________________________________________________________     Note:                                                                         Evaluation of wetting state                                                   ◯ Being wet sufficiently                                          Δ Being wet but insufficiently                                          x Ineffective                                                                 Evaluation of cleanness                                                       ◯ Water spots are not observed.                                   Δ Some water spots are observed but available.                          x Unavailable.                                                           

TEST 18 Removing Effect on Agricultural Chemicals From Foods A) Methodof Preparing Test Samples for Washing

The rind of an apple was cut to pieces approximately equal in thicknessand size. They were fully washed with dilute hydrochloric acid andrepeatedly with water, and dried to obtain clean pieces of the rind ofan apple. Ten ppm of As in the form of As₂ O₃ and DDT was accuratelyattached to the piece.

B) Washing

An 0.5% aqueous soslution of a sample to be tested was prepared. A rindpiece made in A) was washed in the solution at room temperature. Afterthe piece was shaken for 5 minutes, it was put out of the solution andAs and DDT washed down into the washing are determined.

C) Determination of Removing Rate of As

This was determined in accordance with the method for determining As inthe note of the codex on food additives.

D) Determination of Removing Rate of DDT

This was determined in accordance with the method for determiningchloride compounds in the note of the codex on food additives.

E) Evaluation of the Results

⊚: Excellent in removal of the chemicals (a removing rate more than 80%)

◯: Appearent in removal of the same (a removing rate of 50 to 80%)

Δ: Poor in removal of the same (a removing rate of 20 to 50%)

×: The same as in water washing in removal of the same (a removing rateless than 20%)

The results are shown in Table 24.

                  TABLE 24                                                        ______________________________________                                                        Removing  Removing                                            Sample          rate of As                                                                              rate of DDT                                         ______________________________________                                        Test sample 7   ⊚                                                                        ⊚                                    Test sample 22  ⊚                                                                        ◯                                       Comparative     ◯                                                                           ◯                                       test sample 10                                                                Glycine         ◯                                                                           Δ                                             (known detergent                                                              for agricultural                                                              chemicals)                                                                    ______________________________________                                         Note:                                                                         Comparative test sample used is the same one as used in Test 7.          

TEST 19 Effect of Dispersing or Dissolving Sparingly Soluble SurfaceActive Agents

Twenty grams of each of sucrose fatty acid esters [trade name: DK esterF-160 (HLB15) and DK ester F-110 (HLB11) from DAI-ICHI KOGYO SEIYAKUCO., LTD., JAPAN] and soya bean lecithin [trade name: Honen Lecithin AYfrom Honen Seiyu Co., Ltd., JAPAN], which are sparingly soluble surfaceactive agents, and a prescribed amount of a test sample in the form ofpowder were dispersed or dissolved in 200 g of water, and the resultantwas spray-dried to obtain a preparation for testing.

Sucrose fatty acid ester was first moistened and mixed well with a smallamount of water, then the required amount of water was added. Themixture was heated at a temperature of 60° C. to 80° C. to disperse theester. Lecithin was dispersed in a prescribed amount of water.

Twenty grams of palmitic acid monoglyceride in the form of powder (tradename: Sunsoft No. 8001 from Taiyo Kagaku Co., Ltd., JAPAN) and aprescribed amount of a Test sample in the form of powder were mixed witha V type mixer to obtain a preparation for testing.

Ten grams of each of the preparations were added to a beaker containing200 g of warm water at 70° C. and the mixture was slowly stirred at 50rpm using a magnetic stirrer to observe solubility of the preparation.The results are shown in Table 25.

                  TABLE 25                                                        ______________________________________                                                Added                                                                 Sample  Amount (g)                                                                              Surface Active agent                                                                           Evaulation                                 ______________________________________                                        Test  1     5         Sucrose fatty  ⊚                         sample                acid ester (HLB15)                                            4     5         Sucrose fatty  ⊚                                               acid ester (HLB15)                                            6     5         Sucrose fatty  ⊚                                               acid ester (HLB15)                                            13    5         Sucrose fatty  ⊚                                               acid ester (HLB15)                                            16    5         Sucrose fatty  ⊚                                               acid ester (HLB15)                                            18    5         Sucrose fatty  ⊚                                               acid ester (HLB15)                                            19    5         Sucrose fatty  ⊚                                               acid ester (HLB15)                                            21    5         Sucrose fatty  ⊚                                               acid ester (HLB15)                                            23    5         Sucrose fatty  ⊚                                               acid ester (HLB15)                                            6     2         Sucrose fatty  ◯                                                  acid ester (HLB15)                                      Blank       0         Sucrose fatty  x                                                              acid ester (HLB15)                                      Test  1     5         Sucrose fatty  ⊚                         sample                acid ester (HLB11)                                            6     5         Sucrose fatty  ⊚                                               acid ester (HLB11)                                      Blank       0         Sucrose fatty  x                                                              acid ester (HLB11)                                      Test  1     5         Palmitic acid  ⊚                         sample                monoglyceide (HLB3.5)                                         4     5         Palmitic acid  ⊚                                               monoglyceide (HLB3.5)                                         6     5         Palmitic acid  ⊚                                               monoglyceide (HLB3.5)                                         13    5         Palmitic acid  ⊚                                               monoglyceide (HLB3.5)                                         16    5         Palmitic acid  ⊚                                               monoglyceide (HLB3.5)                                         18    5         Palmitic acid  ⊚                                               monoglyceide (HLB3.5)                                         19    5         Palmitic acid  ◯                                                  monoglyceide (HLB3.5)                                         21    5         Palmitic acid  ◯                                                  monoglyceride (HLB3.5)                                        23    5         Palmitic acid  ◯                                                  monoglyceride (HLB3.5)                                  Blank       0         Palmitic acid  x                                                              monoglyceride (HLB3.5)                                  Test  1     5         Lecithin       ⊚                         sample                                                                              4     5         Lecithin       ⊚                               6     5         Lecithin       ⊚                               13    5         Lecithin       ⊚                               16    5         Lecithin       ⊚                               18    5         Lecithin       ⊚                               19    5         Lecithin       ⊚                               21    5         Lecithin       ◯                                  23    5         Lecithin       ◯                            Blank       0         Lecithin       x                                        ______________________________________                                         Evaluation                                                                    ⊚: Uniformly dispersed or dissolved within 1 minute            ◯: Uniformly dispersed or dissolved                               Δ: Producing a small number of massy globules                           x: Producing a large number of massy globules                            

Consideration

It can be seen from the results shown in Table 25 that Test samples ofthe present invention can allow sucrose fatty acid ester, palmitic acidmonoglyceride and lecithin to disperse or dissolve rapidly in water.

TEST 20 Test of Particle Dispersing Property

The following tests were conducted on Test samples prepared in Examplesand Comparative test samples 10 (sucrose fatty acid ester), 11 (soyabean lecithin) and 15 (a polymer of sodium acrylate having a molecularweight of 8,000).

A. Test of the Property which Decreases Viscosity of Calcium CarbonateSlurry Test Method

A total weight 250 g of a Test sample and city water was put into theNational Ml type mixer and then 250 g of calcium carbonate (lightcalcium carbonate from Takehara Kagaku Kogyo Co., Ltd., JAPAN) wereadded. The resultants were mixed for 2 minutes to obtain a 50% by weightslurry.

The slurry was transferred in a beaker and its viscosity was determinedby using the DVH-B type viscometer from TOKYO KEIKI CO., LTD., JAPAN.

B. Test of the Property which Decreases Viscosity of Kaolin Slurry TestMethod

A total weight 200 g of a test sample and city water was put into theNational MI type mixer and then 300 g of kaolin powder (Tsuchya KoalinKogyo Co., Ltd., JAPAN) were added and mixed for 2 minutes to make up 60w/w % slurry.

The viscosity of kaolin slurry was determined by the same manner as A.

Test of the Property which Prevents Sedimentation Test Method

50 ml of 5.0 w/v % calcium carbonate (Takehara Kagaku Kogyo Co., Ltd.,JAPAN, fine flurry) and a test sample were added into a 100 mlcalorimetric glass tube and filled up to 100 ml with water, served astest water.

After mixing well, the test water was left to stand for 5 minutes.

Test aliquot for Ca determination is sampled from the part of 50 mlposition (at the middle part in height).

The dispersibility was calculated with Ca concentration before and afterstanding by the following equation. ##EQU4##

The results are shown in Table 26 wherein the blank spaces mean "notmeasured" or "not tested".

                                      TABLE 26                                    __________________________________________________________________________                    Test sample*                                                                  1  2     3  4  5   6     7  10 11 12                          __________________________________________________________________________    Particle                                                                            Calcium carbonate                                                                       291                                                                              30    1095                                                                             2920                                                                             48  95    140                                                                              4700                                                                             382                                                                              1870                        dispersing                                                                          slurry (cps) (0.2%) 94   (0.2%)                                         property           (0.1%) 396  693                                                  Kaolin slurry                                                                           4200                                                                             2246  331                                                                              1071                                                                             3800                                                                              67    82 1174                                                                             290                                                                              4800                              (cps)                        (0.2%) 70                                                                     (0.1%) 97                                        Sedimentation                                                                              500 ppm 92      500 ppm 91                                       preventing   200 ppm 84      200 ppm 80                                       property (%) 100 ppm 63                                                       (calcium carbonate)                                                     __________________________________________________________________________                      Test sample*                                                                  13 14  15 16  17 18  19 21  22 23                           __________________________________________________________________________    Particle                                                                             Calcium carbonate                                                                        105                                                                              560 295                                                                              1510                                                                              72 210 252                                                                              357 329                                                                              720                          dispersing                                                                           slurry (cps)                                                           property                                                                             Kaolin slurry                                                                            410                                                                              4200                                                                              95 159 2018                                                                             110 152                                                                              1052                                                                              191                                                                              898                                 (cps)                                                                  __________________________________________________________________________                                      Comparative test sample*                                                      No. 10  No. 11                                                                           No. 15                                                                            Blank                        __________________________________________________________________________                      Particle-                                                                           Calcium carbonate                                                                       5860   >8000                                                                             150 >8000                                          dispersing                                                                          slurry (cps)                                                            property                                                                            Kaolin slurry                                                                           4782   >8000                                                                             180 >8000                                                (cps)                                                                         Sedimentation                                                                           1000 ppm 88                                                         preventing property                                                                     500 ppm 60                                                          (%) (calcium carbonate)                                                                 200 ppm 44                                  __________________________________________________________________________     *0.3% of the test sample was used for each case.                         

TEST 21 Effect on Dispersibility of Cocoa Test Method

A prescribed amount of a Test sample was added to 5 g of a commerciallyavailable cocoa powder (Van Houten Cocoa containing 22 to 24% of cocoabutter). The mixture was fully mixed and poured into a 100 ml graduatedcylinder containing 95 g of cold water at 5° C. The cylinder was turnedupside down 20 times and then left for 10 minutes at room temperature.The portion of the added mixture which floats on the upper side wasremoved and its weight was measured.

The dispersibility of cocoa is calculated by the substract of floatingweight from initial weight of cocoa, and expressed in percent of initialvalue.

                  TABLE 27                                                        ______________________________________                                                          Concentration                                                                 (% by weight                                                                  with respect to                                                                            Dispersi-                                      Sample            cocoa)       bility (%)                                     ______________________________________                                        Example  Test sample 5                                                                              0.1          74                                                               0.3          96                                                  Test sample 14                                                                             0.1          78                                                               0.3          98                                                               1.0          100                                                 Test sample 15                                                                             0.3          94                                                  Test sample 21                                                                             0.3          88                                         Not added         --           48                                             Comparative                                                                            Comparative test                                                                           0.1          52                                         example  sample 10    0.3          67                                                  Comparative test                                                                           0.1          48                                                  sample 11    0.3          62                                         Example  Test sample 14 +                                                                           0.08 + 0.02  84                                                  Comparative test                                                                           0.05 + 0.05  88                                                  sample 10    0.02 + 0.08  68                                                  Test sample 14 +                                                                           0.08 + 0.02  81                                                  Comparative test                                                                           0.05 + 0.05  85                                                  sample 11    0.02 + 0.08  64                                         ______________________________________                                    

Consideration

It can be seen from the results of Table 27 that Test samples of thepresent invention are excellent dispersants which can improve thedispersibility of cocoa.

Further, a combination use of Test sample and sucrose fatty acid esteror soybean lecithin shows an excellent dispersibility of cocoa, and alsoa synergistic effect in the dispersibility.

TEST 22

Each of Test samples of the present invention and Comparative testsamples and a combination of them was dissolved in a prescribed amountof city water. To the solution was added 30 g of a liquid insecticide,Sumition (O,O-dimethyl O-4-nitro-m-tolyl phosphorothionate). The mixturewas mixed for 10 minutes using a homomixer. Thus, the preparations 1-16each having a weight of 100 g were obtained.

Test of Stability

The preparation was put in a 50 ml measuring cylinder and left for standat 60° C. for 4 weeks. The suspending rate showing stability of thepreparation is obtained from the following equation. ##EQU5##

The conditions for preparation and the test results are shown in Table28.

                  TABLE 28                                                        ______________________________________                                        No. of                Amount of the                                                                             Suspending                                  preparation                                                                           Sample        test sample (g)                                                                           rate (%)                                    ______________________________________                                        1       Test sample 1 3           92                                          2       Test sample 1 2           85                                          3       Test sample 1 1           73                                          4       Test sample 4 3           84                                          5       Test sample 6 3           90                                          6       Test sample 13                                                                              3           87                                          7       Test sample 16                                                                              3           86                                          8       Test sample 19                                                                              3           82                                          9       Test sample 21                                                                              3           80                                          10      Test sample 23                                                                              3           77                                          11      Comparative   3           63                                                  test sample 10                                                        12      Comparative   3           55                                                  test sample 11                                                        13      Test sample 1 +                                                                             0.2 + 0.8   72                                                  Comparative test                                                              sample 11                                                             14      Test sample 1 +                                                                             0.5 + 0.5   89                                                  Comparative test                                                              sample 11                                                             15      Test sample 1 +                                                                             0.8 + 0.2   78                                                  Comparative test                                                              sample 11                                                             16      Not added     0           52                                          ______________________________________                                    

TEST 23

Each of Test samples of the present invention, Comparative test samplesand a combination of them was dissolved in a prescribed amount of citywater as in Test 22. The solution was put into a ball mill to which 15 gof MBTC (methylene bisthiocyanate) of a solid bactericide were added.Glass beads of 1 mm in diameter were put in the mill and the mixture waswater-ground for 8 hours. Thus, the preparations 17 to 30 having aweight of 100 g each were obtained.

The stability tests on the preparations were conducted in the samemanner as in Test 22. The results are shown in Table 29.

                  TABLE 29                                                        ______________________________________                                        No. of                Amount of test                                                                            Suspending                                  preparation                                                                           Sample        sample (g)  rate (%)                                    ______________________________________                                        17      Test sample 6 3           91                                          18      Test sample 6 1           82                                          19      Test sample 6 0.5         70                                          20      Test sample 13                                                                              3           88                                          21      Test sample 16                                                                              3           85                                          22      Test sample 19                                                                              3           78                                          23      Test sample 21                                                                              3           76                                          24      Test sample 23                                                                              3           73                                          25      Not added     0           30                                          26      Comparative   5           37                                                  test sample 10                                                        27      Comparative   5           45                                                  test sample 11                                                        28      Test sample 6 +                                                                             0.1 + 4     66                                                  Comparative test                                                              sample 10                                                             29      Test sample 6 +                                                                             0.25 + 0.25 85                                                  Comparative test                                                              sample 10                                                             30      Test sample 6 +                                                                             0.4 + 0.1   82                                                  Comparative test                                                              sample 10                                                             ______________________________________                                    

TEST 24

Each of 30 parts of Tsumacide (m-tolylmethylcarbamate, a powderinsecticide) and 30 parts of DCPA (3', 4'-dichloropropionanilide, aherbcide) was mixed with stirring with 5 parts of the sample obtained bydrying Test sample 1 (the same Test sample as used in Test 8) and 65parts of kaolin using a V type mixer to obtain two wettable preparation.Each of the wettable preparations was diluted with water at degree ofdilution of 500, 1,000 and 2,000 folds. The portions of the dilutedpreparations were separately put in a 100 ml graduated cylinder and wereleft for 3 hours.

The states of them were observed and the dispersibility rates werecalculated from the following equation. ##EQU6##

The values of the dispersibility of all the preparations were more than80%.

TEST 25

The preparations 31 to 47 each containing 5% by weight of Fenthion(O,O-dimethyl O-4-methylthio-m-tolylphosphrothionate, a liquidinsecticide) and having a weight of 100 g were prepared in the similarmanner as in Test 21 using Fenthion instead of Sumition.

Test of Stability

The preparation was left standing at 50° C. for one month. Thedecomposition rate of the insecticide in the preparation was determinedby measuring the change of the concentration of the insecticide causedby the preparation being left standing.

The insecticide in the preparation was determined using a FPDgaschromatograph. The results are shown in Table 30.

                  TABLE 30                                                        ______________________________________                                        No. of                Amount of  Decomposition                                preparation                                                                           Sample        sample (g) rate (%)                                     ______________________________________                                        31      Test sample 5 1          1.8                                          32      Test sample 5 0.5        2.6                                          33      Test sample 4 1          3.7                                          34      Test sample 6 1          2.4                                          35      Test sample 6 0.5        4.7                                          36      Test sample 13                                                                              1          2.8                                          37      Test sample 16                                                                              1          2.6                                          38      Test sample 19                                                                              1          4.8                                          39      Test sample 21                                                                              1          5.2                                          40      Test sample 23                                                                              1          6.6                                          41      Comparative test                                                                            2          25.0                                                 sample 10                                                             42      Comparative test                                                                            2          30.0                                                 sample 11                                                             43      Test sample 1 +                                                                             0.1 + 0.4  4.0                                                  Comparative test                                                              sample 11                                                             44      Test sample 1 +                                                                             0.25 + 0.25                                                                              1.7                                                  Comparative test                                                              sample 11                                                             45      Test sample 1 +                                                                             0.4 + 0.1  2.2                                                  Comparative test                                                              sample 11                                                             46      Test sample 1 +                                                                             0.25 + 0.25                                                                              2.1                                                  Comparative test                                                              sample 10                                                             47      Not added     0          36.0                                         ______________________________________                                         TEST 26

2 l of a 2000 ppm aqueous solution of each of Test samples of thepresent invention and such conventional surface active agents as sodiumdodecylbenzenesulfonate, lauryltrimethylammonium chloride andpolyoxyethylenenonylphenylether (n=10) were separately sprayed to ayoung seedling of tomato grown for about 25 days after seeding. Theyoung seedlings were kept in a humid atmosphere for six days and thedegree of damage of them from the sprayed agent was observed. Theresults are shown in Table 31.

Test samples used are the ones desalted and dried as in Test 24.

                  TABLE 31                                                        ______________________________________                                                         Degree of damage of                                          Sample           young tomato seedlings                                       ______________________________________                                        not added        -                                                            Test sample 6    -                                                            Test sample 13   -                                                            Test sample 16   -                                                            Test sample 21   -                                                            Sodium           ±                                                         dodecylbenzenesulfonate                                                       Lauryltrimethylammonium                                                                        ++                                                           chloride                                                                      Polyoxyethylene- +                                                            nonylphenylether                                                              (n = 10)                                                                      ______________________________________                                         Note                                                                          -: No damage.                                                                 ±: The edges of some leaves died.                                          +: Some leaves changed color to brown.                                        ++: Many leaves changed color to brown.                                  

Analytical Results of Test Samples

Amino acid compositions of the test samples 1, 7, 13 and 15 weredetermined. The results are shown in Table 32. Each of the values inTable 32 represents number of grams of the amino acids contained in 100g of the corresponding Test sample.

                  TABLE 32                                                        ______________________________________                                                  Test sample                                                         Amino acid  No. 1   No. 7     No. 13                                                                              No. 15                                    ______________________________________                                        Arginine    1.2     <0.1      <0.1  0.1                                       Lysine      0.7     0.8       0.9   3.6                                       Histidine   1.4     1.5       1.2   1.6                                       Phenylalanine                                                                             4.0     3.7       4.6   3.4                                       Tyrosine    2.6     2.4       3.7   2.6                                       Leucine     5.2     5.1       12.1  5.4                                       Isoleucine  2.8     2.4       2.4   2.6                                       Methionine  1.2     1.1       1.6   0.9                                       Valine      3.1     3.1       3.2   3.4                                       Alanine     2.1     2.3       6.4   3.4                                       Glycine     2.6     3.0       2.4   3.6                                       Proline     10.5    8.4       7.1   3.7                                       Glutamic acid                                                                             27.7    26.4      15.5  11.9                                      Serine      3.4     1.4       1.2   1.1                                       Threonine   1.9     0.7       0.6   0.7                                       Aspartic acid                                                                             2.7     2.5       4.3   7.7                                       Tryptophan  0.7     0.7       0.3   0.9                                       Cysteine    0.6     0.5       0.4   0.3                                       ______________________________________                                    

The ultraviolet and visible light absorption spectrums of Test samples1, 7, 13 and 15 are shown in FIGS. 2a, 3a, 4a and 5a, respectively andthe infrared light absorption spectrums of the same samples are shown inFIGS. 2b, 3b, 4b, and 5b, respectively.

What we claimed is:
 1. A food product comprising:(a) a food-stuff; and(b) a protein partial degradation product that is derived from a grainprotein selected from the group consisting of wheat protein, barleyprotein, corn protein, bean protein, and combinations of the foregoingwherein the protein partial degradation product is a powdercharacterized by:(i) a weight average molecular weight, according to theGel filtration method, of from 670-79,000; (ii) an ultravioletabsorption λmax of from about 260 to about 280 nm and an infraredabsorption of about 1400, 1630, and 3400 cm⁻¹ ; (iii) an isoelectricpoint of from about pH 3.9 to about pH 5.0; (iv) a buffering action suchthat 2-25 ml of IN-hydrochloric acid is required to lower the pH of 100ml of a 5% by weight aqueous solution of the protein partial degradationproduct from 6 to 2; (v) solubility in water and insolubility inmethanol, ethanol, acetone and ethyl ether; (vi) a pale yellow to redbrown color; (vii) showing coloration Xanthoprotein reaction andNinhydrin reaction; (viii) a surface tension-reducing capacity such thatthe surface tension of pure water at 25° C. is reduced to 50 dyne/cm orless, as measured by du Noiiy's tensiometer, by adding 0.1% by weight ofthe protein partial degradation product to the pure water; and (ix) anemulsifying capacity such that 100 g of a mixture of water and soya beanoil, containing at least 30% by weight of soya bean oil, can beemulsified completely by adding 1 g. of the protein partial degradationproduct to the mixture.
 2. A food product as defined in claim 1 whereinthe food-stuff is a starchy food-stuff comprising a grain selected fromthe group consisting of wheat, buckwheat, rice, rye, maize, andcombinations thereof, wherein the partial degradation product comprisesfrom about 0.01 to 5% by weight of the starchy food-stuff.
 3. A foodproduct as defined in claim 2 wherein the partial degradation productcomprises from about 0.05 to 3% by weight of the starchy food-stuff. 4.A food product as defined in claim 3 wherein the partial degradationproduct comprises from about 0.1 to 1% by weight of the starchyfood-stuff.
 5. A food product as defined in claim 1, wherein thefood-stuff is a proteinic food-stuff comprising fish or meat containingnot less than 40% by weight protein and wherein the partial degradationproduct comprises from about 0.05 to 10% by weight of the proteinicfood-stuff.
 6. A food product as defined in claim 5 wherein the partialdegradation product comprises from about 0.5 to 5% by weight of theproteinic food-stuff.
 7. A food product as defined in claim 1 whereinthe food-stuff is a dairy product comprising a dairy substancecomprising solid matters of milk; oil and fats; and water and thepartial degradation product comprises from about 0.02 to 5% by weight ofthe dairy substance.
 8. A food product as defined in claim 7 wherein thepartial degradation product comprises from 0.1 to 2% by weight of thedairy substance.
 9. A food product as defined in claim 1 wherein thefood-stuff is an emulsified oily food-stuff comprising an oily phase andan aqueous phase and the partial degradation product comprises fromabout 0.01 to 5% by weight of the emulsified oily food-stuff.
 10. Anemulsified oily food-stuff as defined in claim 9 wherein the proteindegradation product comprises from about 0.03 to 2% of weight of theemulsified oily food-stuff.